CN116209626A

CN116209626A - Thermally fusible laminated film

Info

Publication number: CN116209626A
Application number: CN202180065672.9A
Authority: CN
Inventors: 泽田峻一; 石井和臣
Original assignee: Mitsui Chemicals Tohcello Inc
Current assignee: RM Dongsailu Co.,Ltd.
Priority date: 2020-09-30
Filing date: 2021-09-28
Publication date: 2023-06-02
Also published as: TW202220844A; KR20230052301A; WO2022071289A1

Abstract

The present invention provides a polyethylene laminated film which is suitable for use in packaging bags and the like, has excellent tear properties while maintaining excellent properties such as mechanical strength and blocking resistance, has further improved mechanical strength such as young's modulus while maintaining excellent properties such as blocking resistance, and has excellent lamination strength with an outer layer side film while maintaining excellent properties such as seal strength and impact resistance, and also has excellent blocking resistance. This object is achieved by a laminated film comprising: the laminated film comprising (A) a heat-seal layer, (B) an intermediate layer and (C) a laminated layer of linear low-density polyethylene derived from petroleum, wherein at least one of the (A) heat-seal layer, (B) the intermediate layer and (C) the laminated layer comprises a plant-derived biopolyethylene.

Description

Thermally fusible laminated film

Technical Field

The first invention relates to a polyethylene-based laminated film, and more specifically, to a laminated film which is suitable for use as a packaging film for a bag with a tear port, a bag with a clip chain, or the like, is excellent in tearing property, and is reduced in environmental load by using a resin derived from a plant.

The second invention of the present application relates to a polyethylene-based laminated film, and more specifically, to a laminated film which is suitable for use as a packaging film, is excellent in strength (young's modulus), and is reduced in environmental load by using a plant-derived resin.

The third invention relates to a polyethylene-based laminated film, and more specifically, to a laminated film which is suitable as a packaging film, has excellent lamination strength and blocking resistance with an outer layer side film, and is reduced in environmental load by using a plant-derived resin.

Background

Packaging bags formed by heat-sealing plastic multilayer films are widely used for accommodating various contents such as foods, beverages, detergents, shampoos, cosmetics, and the like. Various polyethylene laminated films having a three-layer structure including a heat-seal layer and a lamination layer in which a base film is laminated on the outside of the heat-seal layer from the inside have been proposed as films on the inside of a heat-seal portion constituting such a plastic multilayer film (for example, refer to patent document 1). These laminated films are designed to have suitable characteristics from the viewpoints of seal strength, impact resistance, blocking resistance, and the like.

As an important aspect of the package, there is a package with a tear port and a package with a clip chain. In the package bag with a tear port and the package bag with a clip chain, the bag is generally torn at the time of opening, and thus a film having moderate tearability (without excessive tearing strength) is required.

In addition, various laminated films of a three-layer structure including a heat-seal layer and a lamination layer in which a base film (base layer) is laminated on the outside of the heat-seal layer from the inside have been proposed as films on the inside of a heat-seal portion constituting a plastic multilayer film (for example, refer to patent document 1). These laminated films are designed to have suitable properties from the viewpoints of seal strength, impact resistance, blocking resistance, etc., but when used in a stand-up pouch (Standing pouch), etc., laminated films having higher mechanical strength are strongly demanded.

In addition, various laminated films of a three-layer structure including a heat-seal layer laminated from the innermost layer side and a laminated layer in which a base film (base layer) is laminated on the outer side thereof have been proposed as films constituting an inner layer of a heat-seal portion of a plastic multilayer film (for example, refer to patent document 1). These laminated films are designed to have suitable properties from the viewpoints of seal strength, impact resistance, blocking resistance, and the like, but in recent years, improvement of lamination strength of the outer layer side film and further improvement of blocking resistance have been demanded.

[ Prior Art literature ]

[ patent literature ]

[ patent document 1] Japanese patent application laid-open No. 2005-14461.

Disclosure of Invention

[ problem to be solved by the invention ]

In view of the above-described technical background, an object of the first invention of the present application is to provide a polyethylene-based laminated film suitable for use in packaging bags and the like, which is excellent in tearability while maintaining excellent properties such as mechanical strength and blocking resistance.

In view of the above-described technical background, an object of the second invention of the present application is to provide a laminated film of polyethylene type suitable for use in packaging bags and the like, in which mechanical strength such as young's modulus is further improved while maintaining excellent properties such as blocking resistance.

In view of the above-described technical background, an object of the third invention of the present application is to provide a polyethylene-based laminated film suitable for use in packaging bags and the like, which is excellent in lamination strength with an outer layer side film and also excellent in blocking resistance while maintaining excellent properties such as seal strength and impact resistance.

[ means for solving the problems ]

The present inventors have studied carefully and found that the present invention has: the first invention of the present application was completed by adding a low-density polyethylene derived from biomass (bio) to at least one of the layers of a laminate film comprising a heat-welded layer, an intermediate layer and a laminate layer of a linear low-density polyethylene derived from petroleum, respectively, to thereby obtain a packaging bag excellent in tear strength.

That is, the first invention of the present application relates to:

[1]

a laminated film, comprising: the heat-sealed layer (1A), the intermediate layer (1B) and the laminated layer (1C) each containing a linear low-density polyethylene derived from petroleum, wherein at least one of the heat-sealed layer (1A), the intermediate layer (1B) and the laminated layer (1C) contains 3 mass% or more of a plant-derived biopolyethylene.

The following [2] to [7] are preferred embodiments of the first invention of the present application.

[2]

The laminated film according to [1], wherein the heat of fusion ΔH calculated from the melting curve obtained by DSC measurement at 0℃to 130℃is 135 to 164J/g.

[3]

The laminated film according to [1] or [2], wherein the plant-derived biopolyethylene has a molecular weight distribution Mw/Mn of 3.5 or more.

[4]

The laminated film according to any one of [1] to [3], wherein the (1D) base material layer is provided on the side of the (1C) laminated layer directly or via the adhesive layer.

[5]

A packaging bag composed of the laminated film according to any one of [1] to [4 ].

[6]

The packaging bag according to [5], which is a packaging bag with a tearing opening.

[7]

The packaging bag according to [5], which is a clip chain packaging bag.

The present inventors have studied carefully and found that the present invention has: in the laminated film including the heat-welded layer, the intermediate layer and the laminated layer of the linear low-density polyethylene derived from petroleum, the young's modulus is remarkably improved by adding the low-density polyethylene derived from biomass to the intermediate layer, and thus the second invention of the present application is completed.

That is, the second invention of the present application relates to:

[8]

a laminated film, comprising: the heat-sealing layer (2A), the intermediate layer (2B) and the laminated layer (2C) respectively contain linear low-density polyethylene derived from petroleum, wherein the intermediate layer (2B) contains plant-derived biopolyethylene.

The following [9] to [14] are preferred embodiments of the second invention of the present application.

[9]

The laminated film according to [8], wherein the heat of fusion ΔH calculated from the melting curve obtained by DSC measurement at 0℃to 130℃is 135 to 164J/g.

[10]

The laminated film according to [8] or [9], wherein the plant-derived biopolyethylene has a molecular weight distribution Mw/Mn of 3.5 or more.

[11]

The laminated film according to any one of [8] to [10], wherein the (2A) heat-welded layer, (2B) intermediate layer and (2C) laminated layer each contain a plant-derived biopolyethylene.

[12]

The laminated film according to any one of [8] to [11], wherein the (2D) base material layer is provided on the side of the (2C) laminated layer directly or via the adhesive layer.

[13]

A packaging bag comprising the laminated film according to any one of [8] to [12 ].

[14]

A self-standing pouch comprising the laminated film according to any one of [8] to [12 ].

The present inventors have studied carefully and found that the present invention has: in the laminated film including the heat-welded layer, the intermediate layer, and the laminated layer of the linear low-density polyethylene derived from petroleum, the addition of the linear low-density polyethylene derived from biomass to at least one of these layers significantly improves the lamination strength and improves the blocking resistance, and thus the third invention of the present application is completed.

That is, the third invention of the present application relates to:

[15]

a laminated film, comprising: the laminated film comprising (3A) a heat-sealed layer, (3B) an intermediate layer and (3C) a laminated layer of linear low-density polyethylene derived from petroleum, wherein at least one of the (3A) heat-sealed layer, (3B) the intermediate layer and (3C) the laminated layer contains at least 3% or more of a plant-derived linear low-density polyethylene.

The following [16] to [20] are preferred embodiments of the third invention of the present application.

[16]

The laminated film according to [15], wherein the (3C) laminated layer contains at least 3% or more of a plant-derived biomass linear low-density polyethylene.

[17]

The laminated film of [15] or [16], wherein the heat of fusion ΔH of 0℃to 130℃calculated from the melting curve obtained by DSC measurement is 135 to 164J/g.

[18]

The laminated film according to any one of [15] to [17], wherein the plant-derived biomass linear low-density polyethylene has a molecular weight distribution Mw/Mn of 3.5 or more.

[19]

The laminated film according to any one of [15] to [18], wherein a (3D) base material layer is provided on the side of the (3C) laminated layer directly or via an adhesive layer.

[20]

A packaging bag comprising the laminated film according to any one of [15] to [19 ].

[ Effect of the invention ]

The laminated film of the first invention can be suitably used in various applications including packaging bags such as a tear-off packaging bag and a clip-chain packaging bag, while maintaining excellent properties of conventional polyethylene laminated films such as mechanical strength and blocking resistance, and while greatly improving tearability, and while reducing environmental load during production thereof.

The laminated film according to the second aspect of the present invention has a significantly improved young's modulus while maintaining the excellent properties of conventional polyethylene laminated films such as blocking resistance, and is also reduced in environmental load during production thereof, and has practically high value properties at a high level exceeding the limit of the prior art, and is suitable for use in various applications including packaging bags such as self-standing bags.

The laminated film according to the third aspect of the present invention has a high level exceeding the limit of the prior art and practically high value properties, and can be suitably used in various applications including packaging bags, while the laminated film has a greatly improved lamination strength and the like while maintaining the excellent properties of conventional polyethylene laminated films such as seal strength and impact resistance, and also has a reduced environmental load during production thereof.

Detailed Description

Embodiments of the first invention of the present application are specifically described below.

The first aspect of the present invention is a laminated film comprising: the laminated film comprising (1A) a heat-sealed layer, (1B) an intermediate layer and (1C) a laminated layer of linear low-density polyethylene derived from petroleum, wherein at least one of the (1A) heat-sealed layer, (1B) the intermediate layer and (1C) the laminated layer contains 3 mass% or more of plant-derived biopolyethylene.

That is, the laminated film of the first invention of the present application contains linear low density polyethylene derived from petroleum in each of the (1A) heat-seal layer, (1B) intermediate layer and (1C) laminated layer.

The laminated film of the first invention of the present application contains a predetermined amount of plant-derived biopolyethylene in at least one of the (1A) heat-sealed layer, the (1B) intermediate layer, and the (1C) laminated layer.

Linear low density polyethylene from petroleum

The linear low density polyethylene derived from petroleum used in the first invention of the present application is a homopolymer of ethylene produced using petroleum as a raw material or a copolymer of ethylene and an α -olefin produced using petroleum as a raw material, and may be synthesized by a generally known production method.

The alpha-olefin may be a compound having 3 to 20 carbon atoms, and examples thereof include: propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like, and mixtures of these may also be used. The alpha-olefin is more preferably a compound of 4, 6 or 8 carbon atoms or a mixture of these, 1-butene, 1-hexene, 1-octene or a mixture of these.

The linear low density polyethylene derived from petroleum is commercially available, and may be obtained by using 2040F (C6-LLDPE, MFR;4.0, density; 0.918 g/cm) manufactured by Ube-Maruzen Polyethylene Co., ltd ³ )。

The density of the linear low density polyethylene derived from petroleum is preferably 0.905 to 0.935g/cm ³ Particularly preferably from 0.915 to 0.930g/cm ³ The MFR is more preferably 0.5 to 6.0g/10 min, particularly preferably 2.0 to 4.0g/10 min.

The molecular weight distribution (expressed as the ratio of weight average molecular weight: mw to number average molecular weight: mn: mw/Mn) of the linear low density polyethylene derived from petroleum is preferably in the range of 1.5 to 4.0, more preferably in the range of 1.8 to 3.5. This Mw/Mn can be determined by gel permeation chromatography (GPC: gel Permeation Chromatography).

The linear low density polyethylene derived from petroleum has 1 to more sharp peaks as measured from an endothermic curve of a differential scanning calorimeter (DSC: differential Scanning Calorimeter) at a heating rate of 10 ℃/min, and the peak has a highest temperature, that is, a melting point, of preferably 95 to 140 ℃, more preferably in the range of 105 to 130 ℃.

The linear low density polyethylene derived from petroleum can be produced by a conventionally generally known production method using: catalysts generally known in the past include multi-site catalysts such as Ziegler catalysts (Ziegler catalysts) and single-site catalysts such as metal-aromatic (Metallocene) catalysts. From the viewpoint of obtaining a linear low-density polyethylene which can form a film having a narrow molecular weight distribution and a high strength, it is more preferable to use a single-site catalyst.

The single-site catalyst is a catalyst capable of forming a uniform active species, and is usually prepared by bringing a metal-aromatic transition metal compound or a non-metal-aromatic transition metal compound into contact with an activating assist catalyst. Compared with the multi-active-site catalyst, the single-active-site catalyst has a uniform active-site structure, so that a polymer having a high molecular weight and a high uniformity structure can be polymerized, which is preferable. The single-site catalyst is particularly preferably a metal aromatic catalyst. The metal aromatic catalyst comprises: a catalyst comprising a transition metal compound of group IV of the periodic Table having a ligand of cyclopentadienyl skeleton, a co-catalyst, optionally an organometallic compound, and each catalyst component of the carrier.

In the above transition metal compound of group IV of the periodic Table containing a ligand having a cyclopentadienyl skeleton, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group or the like. The substituted cyclopentadienyl group is a group having at least one substituent selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms, a silane group-substituted alkyl group, a silane group-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group, a halogen group, a haloalkyl group, a halosilane group, and the like. The substituent of the substituted cyclopentadienyl group may have 2 or more, and in addition, the substituents may bond to each other to form a Ring, thereby forming an indene Ring (Indenyl Ring), a fluorene Ring (Fluorenyl Ring), an Azulenyl Ring (Azulenyl Ring), a hydrogenated body thereof, and the like. The rings formed by bonding substituents to each other may further have substituents to each other.

Among the transition metal compounds of group IV of the periodic Table containing a ligand having a cyclopentadienyl skeleton, zirconium, titanium, hafnium, etc., particularly zirconium, hafnium, etc., are cited as the transition metal. The transition metal compound generally has 2 ligands having a cyclopentadienyl skeleton, and each of the ligands having a cyclopentadienyl skeleton is preferably bonded to each other through a crosslinking group. Further, crosslinking groups may be exemplified by: substituted Silylene groups such as alkylene group, silylene group (Silylene), dialkylsilylene group and diarylidene group having 1 to 4 carbon atoms, substituted germylene groups such as dialkylgermylene group (Dialkyl Germylene) and diarylidene group, and the like. More preferably a substituted silylene group.

Among the transition metal compounds of group IV of the periodic Table, ligands other than those having a cyclopentadienyl skeleton are representatively exemplified: hydrogen, a hydrocarbon group of 1 to 20 carbon atoms (alkyl group, alkenyl group, aryl group, alkylaryl group, arylalkyl group, polyalkenyl group, etc.), halogen, methylalkyl group, methylaryl group, etc.

The above-mentioned transition metal compound of group IV of the periodic Table containing a ligand having a cyclopentadienyl skeleton may be used as the catalyst component, either one or a mixture of two or more.

By co-catalyst is meant that the transition metal compound of group IV of the periodic Table is effectively formed into a polymerization catalyst or that ionic charge in an activated state on the catalyst is made uniform. The auxiliary catalyst can be exemplified by: benzene-soluble Aluminoxane (Aluminoxane) or benzene-insoluble organoaluminum oxy compound of organoaluminum oxy compound, ion-exchange layered silicate, boron compound, ionic compound composed of cation with or without active hydrogen group and noncoordinating anion, lanthanoid (Lanthanoid) salt such as lanthanum oxide, tin oxide, phenoxy compound with fluorine group, etc.

The transition metal compound of group IV of the periodic Table containing a ligand having a cyclopentadienyl skeleton may be used as a carrier for supporting an inorganic or organic compound. The support is more preferably a porous oxide of an inorganic or organic compound, and specifically, examples thereof include: montmorillonite (Montprillonite) plasma-exchanging layered silicate, siO ₂ 、Al ₂ O ₃ 、MgO、ZrO ₂ 、TiO ₂ 、B ₂ O ₃ 、CaO、ZnO、BaO、ThO ₂ Etc. or mixtures of these.

In addition, the optionally used organometallic compound may be exemplified by an organoaluminum compound, an organomagnesium compound, an organozinc compound, and the like. Among these, organoaluminum is suitably used.

The linear low density polyethylene derived from petroleum may be used singly or in combination of two or more. In addition, other polymers, including other vinyl polymers, may also be used in conjunction.

The linear low-density polyethylene derived from petroleum may optionally be formulated with various generally known additives which are usually added to olefin polymers, such as antioxidants, weather stabilizers, antistatic agents, antifoggants, antiblocking agents, slip agents (slip agents) and the like, within a range not detracting from the object of the first invention of the present application.

Plant-derived biopolyethylene

The plant-derived biopolyethylene used in the first invention of the present application is a polyethylene obtained by polymerizing ethylene produced using a plant as a raw material.

In the first aspect of the present invention, the plant-derived biopolyethylene may be any of high-density polyethylene, low-density polyethylene and linear low-density polyethylene, and is more preferably low-density polyethylene or linear low-density polyethylene, and particularly preferably low-density polyethylene.

The polyethylene from the plant may be a commercial product, and for example, a commercially available polyethylene manufactured by Braskem corporation may be used. Specifically, SL218 and SPB681 () can be suitably used.

The plant-derived biopolyethylene used in the first invention is obtained by polymerizing a monomer containing ethylene derived from a living body. The biomass-derived ethylene is preferably ethylene obtained by the following production method, but is not limited thereto. Further, since ethylene derived from biomass is used as a monomer of the raw material, the polyethylene system polymerized is derived from biomass. The raw material monomer of the polyethylene may not contain 100% by mass of ethylene derived from a living organism, and may contain ethylene not derived from a living organism or a raw material monomer other than ethylene.

The method for producing the biomass ethylene, which is a raw material of the plant-derived biomass polyethylene, is not particularly limited, and it can be obtained by a conventionally generally known method. An example of a method for producing bioethylene will be described below.

The biomass ethylene can be produced from ethanol derived from biomass as a raw material. Particularly preferred is the use of biomass-derived fermented ethanol obtained from plant material. The plant material is not particularly limited, and conventionally known plants can be used. Examples include corn, sugar cane, sugar beet and cassava.

In the first invention of the present application, the term "biomass-derived fermented ethanol" means ethanol obtained by bringing a microorganism producing ethanol or a product derived from a crushed product thereof into contact with a culture medium containing a carbon source obtained from a plant material, and purifying the resulting culture medium after production. The purification of ethanol from the culture solution may be carried out by a conventionally known method such as distillation, membrane separation and extraction. Examples thereof include a method of adding benzene, cyclohexane, etc. and azeotroping them, and a method of removing water by membrane separation, etc.

In order to obtain bioethylene, high-level purification can be further performed at this stage so that the total amount of impurities in ethanol becomes 1ppm or less.

When ethylene is obtained by dehydration of ethanol, a catalyst is usually used, and the catalyst is not particularly limited, and a conventionally known catalyst can be used. In the process, a fixed bed flow-through reaction is advantageous in that separation of the catalyst and the product is easily performed, and for example, gamma-alumina is more preferable.

Since this dehydration reaction is an endothermic reaction, it is usually carried out under heating. The heating temperature is not limited as long as the reaction is carried out at a commercially useful reaction rate, and is preferably 100℃or higher, more preferably 250℃or higher, and still more preferably 300℃or higher. The upper limit is not particularly limited, and is preferably 500℃or less, more preferably 400℃or less, from the viewpoints of energy balance and equipment.

The reaction pressure is also not particularly limited, and is preferably a pressure of not less than normal pressure in order to facilitate the subsequent gas-liquid separation. The fixed bed flow-through reaction in which the separation of the catalyst is easily performed is industrially preferable, but may be a liquid-phase suspension bed, a fluidized bed, or the like.

In the dehydration reaction of ethanol, the yield of the reaction is about the amount of water contained in ethanol supplied as a raw material. In general, in the case of performing a dehydration reaction, anhydrous is preferable in consideration of the efficiency of removing water. However, in the case of dehydration reaction of ethanol using a solid catalyst, it has been known that the amount of other olefins, particularly butenes, produced tends to increase when water is not present. This is presumed to be because if a small amount of water is not present, dimerization of dehydrated ethylene may not be suppressed. The lower limit of the allowable water content is necessarily 0.1 mass% or more, and more preferably 0.5 mass% or more. The upper limit is not particularly limited, but is preferably 50 mass% or less, more preferably 30 mass% or less, and still more preferably 20 mass% or less, from the viewpoint of physical balance and thermal balance.

The dehydration reaction of ethanol is performed in this manner to obtain a mixed component of ethylene, water and a small amount of unreacted ethanol, and since ethylene is a gas at room temperature and about 5MPa or less, water and ethanol can be removed from the mixed component by gas-liquid separation to obtain ethylene. This method can be carried out by a generally known method.

The ethylene obtained by the gas-liquid separation is further distilled, and the distillation method, the operation temperature, the residence time, and the like are not particularly limited, except that the operation pressure at this time is not less than normal pressure.

When the raw material is biomass-derived fermented ethanol, the ethylene obtained contains a very small amount of carbonic acid gas which is a carbonyl compound or a decomposition product thereof, such as ketone, aldehyde, or ester, which is an impurity mixed in the ethanol fermentation step, or ammonia which is a decomposition product of ferment, a nitrogen-containing compound or a decomposition product thereof, such as amine or amino acid, which is an impurity. In the production or use of polyethylene, these very small amounts of impurities can be removed by refining because of the problematic concerns. The purification method is not particularly limited, and may be carried out by a conventionally known method. Suitable purification operations include, for example, adsorption purification methods. The adsorbent to be used is not particularly limited, and conventionally known adsorbents can be used. More preferably, the adsorbent is a material having a high surface area, and the type of the adsorbent is selected in accordance with the type and amount of impurities in ethylene obtained by dehydration reaction of biomass-derived fermented ethanol.

Further, the method of purifying impurities in ethylene may be combined with caustic water treatment. In the case of caustic water treatment, it is more preferable to conduct the treatment before the adsorption purification. In this case, after the caustic treatment, a water removal treatment must be performed before the adsorption purification.

The monomer used as a raw material of the plant-derived biopolyethylene may further contain ethylene and/or α -olefin derived from fossil fuel, or may further contain α -olefin derived from biomass.

The carbon number of the α -olefin is not particularly limited, and a carbon number of 3 to 20 is usually used, and butene, hexene or octene is more preferable. This is because butene, hexene or octene can be produced by polymerizing ethylene as a raw material derived from biomass. Further, by containing such an α -olefin, the polyolefin polymerized has an alkyl group as a branched structure, and can be configured to be a polyolefin rich in flexibility as compared with a simple linear polyolefin.

The polyethylene is more preferably an ethylene homopolymer. This is because ethylene, which is a raw material derived from biomass, can be theoretically produced from 100% of components derived from biomass.

The concentration of ethylene derived from biomass (hereinafter sometimes referred to as "biomass") in the polyethylene is determined by radioactive carbon [ ] ¹⁴ C) Is a value obtained by measuring the content of biomass-derived carbon. It is known that the carbon dioxide in the atmosphere contains the carbon dioxide at a certain ratio (105.5 pMC) ¹⁴ C, plants grown so as to receive carbon dioxide from the atmosphere, e.g. from maize ¹⁴ The C content was also about 105.5pMC. In addition, it is hardly contained in fossil fuels ¹⁴ C is also known. Thus, by measuring the total carbon atoms contained in the polyethylene ¹⁴ The ratio of C can be calculated as the ratio of carbon from the biomass. In the first invention of the present application, in the polyethylene ¹⁴ The content of C is set to P _14C In the case of (2), the content P of biomass-derived carbon _bio This can be obtained in the following manner.

P _bio (％)＝P _14C /105.5×100

In the biomass polyethylene used in the first invention of the present application, theoretically, if all of the ethylene derived from the biomass is used as a raw material of the polyethylene, the ethylene concentration from the biomass is 100%, and the degree of the biomass-derived polyethylene is 100%. Further, the concentration of ethylene derived from biomass in the polyethylene derived from fossil fuel produced only from the raw material derived from fossil fuel was 0%, and the degree of biomass of the polyethylene derived from fossil fuel was 0%.

In the first invention of the present application, the degree of biology of the biopolyethylene is not necessarily 100%. This is because the amount of fossil fuel can be reduced as compared with the prior art even if a raw material derived from biomass is used for a part of the biomass polyethylene.

The method for polymerizing the monomer containing ethylene derived from the biomass in the biopolyethylene used in the first invention of the present application is not particularly limited, and may be carried out by a conventionally known method. The polymerization temperature or polymerization pressure may be appropriately adjusted depending on the polymerization method or polymerization apparatus. The polymerization apparatus is not particularly limited, and conventionally known apparatuses can be used.

For example, the polymerization method of the ethylene-containing monomer described below can be applied.

The polymerization method of the living polyethylene may be appropriately selected depending on the kind of the intended polyethylene, for example, the density or branching of the High Density Polyethylene (HDPE), the Medium Density Polyethylene (MDPE), the Low Density Polyethylene (LDPE), the Linear Low Density Polyethylene (LLDPE), and the like. For example, it is more preferable to use a multi-site catalyst such as a chiffon catalyst or a phillips catalyst (Phillips Catalyst) or a single-site catalyst such as a metal aromatic catalyst as a polymerization catalyst, and to carry out the polymerization in 1 or 2 stages or more by any one of gas-phase polymerization, slurry polymerization, solution polymerization and high-pressure ion polymerization.

From the viewpoint of obtaining a biomass polyethylene having a wide molecular weight distribution and excellent flexibility and moldability, it is more preferable to use a multi-site catalyst such as a chiffon catalyst or a phillips catalyst.

A more preferred chiffon catalyst is a generally known chiffon catalyst used for coordination polymerization of ethylene and α -olefin, and examples thereof include: a catalyst comprising a titanium compound and an organoaluminum compound, and a catalyst comprising a titanium halide compound and an organoaluminum compound; a catalyst comprising a solid catalyst component comprising titanium, magnesium, chlorine or the like and an organoaluminum compound. More specifically, such catalysts may be exemplified: a catalyst comprising a catalyst component (a) obtained by reacting a titanium compound with a reaction product of an alcohol pretreatment of anhydrous magnesium dihalide and an organometallic compound, and an organometallic compound (b); a catalyst comprising a catalyst component (A) obtained by reacting magnesium metal with an oxygen-containing organic compound such as an organic compound for hydrogen oxidation or magnesium, an oxygen-containing organic compound for transition metal, and an aluminum halide, and a catalyst component (B) of an organometallic compound; a catalyst comprising (i) at least one oxygen-containing organic compound selected from the group consisting of metallic magnesium and an organic compound of hydrogen oxide, magnesium, and a halogen-containing compound, (ii) at least one oxygen-containing organic compound selected from the group consisting of a transition metal and a halogen-containing compound, (iii) a reactant obtained by reacting a silicon compound, and (iv) a solid catalyst component (A) obtained by reacting an aluminum halide compound, and (B) a catalyst component of an organometallic compound.

The phillips catalyst may be a generally known phillips catalyst used for the coordination polymerization of ethylene or an α -olefin, and examples thereof include a catalyst system containing a chromium compound such as chromium oxide, and specifically, examples thereof include: and a catalyst in which a chromium compound such as chromium trioxide or chromate is supported on a solid oxide such as silica, alumina, silica-alumina or silica-titania.

The density of the plant-derived biopolyethylene is not particularly limited, and is preferably 0.905 to 0.935g/cm ³ Particularly preferably from 0.915 to 0.930g/cm ³ I.e. the following. The plant-derived biopolyethylene is preferably a low density polyethylene or a linear low density polyethylene.

The MFR of the plant-derived biopolyethylene is also not particularly limited, but is preferably from 0.3 to 15.0g/10 min, particularly preferably from 1.0 to 12.0g/10 min, more preferably from 1.5 to 10.0g/10 min, particularly preferably from 2.0 to 9.0g/10 min, from the viewpoint of moldability and the like.

The molecular weight distribution of the plant-derived biopolyethylene is also not particularly limited, and from the viewpoints of flexibility, moldability and the like, the molecular weight distribution (expressed as a ratio of weight average molecular weight: mw to number average molecular weight: mn: mw/Mn) is more preferably 3.5 or more, particularly preferably 3.8 to 9.0, and still more preferably in the range of 4.0 to 8.6. This Mw/Mn can be measured by Gel Permeation Chromatography (GPC), and more specifically, can be measured by, for example, the methods described in the examples of the present application.

In addition, the plant-derived biopolyethylene has 1 to more sharp peaks in an endothermic curve measured by a Differential Scanning Calorimeter (DSC) at a heating rate of 10 ℃/min, and the peak has a highest temperature, that is, a melting point, of more preferably 95 to 140 ℃, and still more preferably in the range of 100 to 135 ℃.

The plant-derived biopolyethylene may be used singly or in combination of two or more. In addition, other vinyl polymers may be used in combination with other polymers.

Various generally known additives, such as antioxidants, weather stabilizers, antistatic agents, antifoggants, antiblocking agents, slip agents (slip agents) and the like, which are usually added to olefin polymers, can be optionally formulated into the plant-derived biopolyethylene within a range not detracting from the object of the first invention of the present application.

The laminated film of the first invention of the present application has (1A) a heat-seal layer, (1B) an intermediate layer, and (1C) a laminated layer described below.

(1A) The heat-welded layer, the (1B) intermediate layer and the (1C) laminated layer all contain the linear low-density polyethylene derived from petroleum. By making the heat-welded layer (1A), the intermediate layer (1B) and the laminated layer (1C) each contain the linear low-density polyethylene derived from petroleum, the lamination strength between the layers can be made sufficient. Further, the laminated film is advantageous from the viewpoint of productivity and cost.

(1A) Thermal fusion layer

When the packaging bag is formed using the laminated film according to the first aspect of the present invention, the heat-seal layer (1A) constituting the laminated film according to the first aspect of the present invention is often formed as the innermost layer and is welded to another film. Therefore, it is preferable to use a low melting point resin in order to obtain high sealing strength. For example, by setting the ethylene content of the linear low-density polyethylene derived from petroleum to be low, the melting point of the heat-seal layer (1A) can be reduced. More specifically, the ethylene content of the linear low-density polyethylene derived from petroleum is preferably 10 mass% or less, more preferably 7 mass% or less, and even more preferably 5 mass% or less.

When the ethylene content of the linear low-density polyethylene derived from petroleum has to be increased due to the strength of the film or the necessity of using a material common to other layers, etc., a low-melting resin may be added to the (1A) heat-welded layer. In the case where the plant-derived biopolyethylene is added to the heat-sealed layer (1A), the plant-derived biopolyethylene having a low melting point may be added.

The other low-melting point resins mentioned above can be exemplified by: ethylene-based polymers having a relatively low density such as high-pressure low-density polyethylene and ethylene- α -olefin random copolymer; and an adhesion-imparting resin such as an aliphatic hydrocarbon resin, a alicyclic hydrocarbon resin, an aromatic hydrocarbon resin, a polyterene (polyterene) resin, a rosin-based resin, a styrene-based resin, and a Coumarone (Coumarone) -Indene (index) resin.

The linear low-density polyethylene derived from petroleum in the heat-seal layer (1A) is preferably contained in an amount of 50 mass% or more, more preferably 55 to 99 mass%, particularly preferably 65 to 95 mass%, from the viewpoint of heat sealability and the like.

The content of the plant-derived biopolyethylene in the heat-seal layer (1A) is preferably 1% by mass or more, more preferably 5 to 40% by mass, particularly preferably 7 to 30% by mass, from the viewpoint of tearability and the like.

(1A) The thickness of the heat-seal layer is not particularly limited, but is preferably 5 μm or more, and more preferably 10 μm or more, from the viewpoint of heat sealability and the like.

On the other hand, from the viewpoint of film strength and the like, it is more preferably 30 μm or less, and particularly preferably 20 μm or less.

Various commonly known additives, such as an antiblocking agent, a slip agent (slip agent), an antioxidant, a weather-resistant stabilizer, an antistatic agent, an antifogging agent, etc., which are generally added to polyolefin, may be optionally blended into the heat-sealing layer within a range not detracting from the object of the first invention of the present application.

The anti-caking agent may be exemplified by: silica, talc, silica, clay, calcium carbonate, synthetic zeolite, starch, alumina, acrylic resin, methacrylic resin, silicone resin, polytetrafluoroethylene resin, and the like.

Further, a slip agent may be exemplified: various amides such as palmitamide, stearamide, oleamide, erucamide, oil palmitamide, stearpalmitamide, methylenebisstearamide, methylenebisoleamide, ethylenebisoleamide, and ethylenebiserucamide; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; hydrogenated castor oil, etc.

(1B) Intermediate layer

Among the layers constituting the laminated film of the first invention of the present application, (1A) the heat-seal layer is preferably designed so as to obtain an appropriate seal strength, and (1C) the laminated layer is preferably designed in consideration of the lamination strength with (1D) the base material layer and the like, whereas (1B) the limitation of the intermediate layer is relatively small, so that desired physical properties such as mechanical properties and performance can be preferentially imparted to the entire laminated film of the first invention of the present application. In this case, the thickness of the intermediate layer (1B) is preferably set to be larger than the thickness of the heat-seal layer (1A) and the thickness of the laminated layer (1C), and particularly preferably set to be larger than the sum of the thickness of the heat-seal layer (1A) and the thickness of the laminated layer (1C).

More specifically, the thickness of the intermediate layer (1B) is more preferably 10 μm or more, particularly preferably 15 μm or more, and particularly preferably 30 μm or more.

On the other hand, from the viewpoint of heat sealability and the like, the thickness of the intermediate layer (1B) is preferably 150 μm or less, more preferably 130 μm or less, still more preferably 100 μm or less, and particularly preferably 90 μm or less.

For example, from the viewpoint of achieving high mechanical strength for the entire laminate, the (1B) intermediate layer is more preferably a resin having high mechanical strength at a high ratio. For example, a resin having a high molecular weight and a narrow molecular weight distribution is selected as the linear low density polyethylene derived from petroleum, and the content is more preferably set to be high.

From this viewpoint, the content of the linear low-density polyethylene derived from petroleum in the heat-seal layer (1A) is more preferably 50% by mass or more, particularly preferably 75 to 100% by mass, particularly preferably 85 to 100% by mass, and particularly preferably 90 to 100% by mass.

The molecular weight distribution of the linear low-density polyethylene derived from petroleum is preferably 4.0 or less, and particularly preferably 3.0 or less. Similarly, the linear low-density polyethylene derived from petroleum has a molecular weight of 20000 or more, more preferably 25000 or more, still more preferably 50000 or more, and particularly preferably 70000 or more.

From the viewpoint of improving flexibility and impact resistance of the entire laminate, the intermediate layer (1B) is preferably a resin having high flexibility and impact resistance at a high ratio. For example, a resin having high flexibility and impact resistance may be selected as the linear low density polyethylene derived from petroleum, and the content may be further set to be high.

Further, the flexibility and impact resistance of the intermediate layer (1B) can be improved by adding an elastomer or rubber component to the intermediate layer (1B), and the flexibility and impact resistance of the entire laminate can be improved. Examples of the elastomer or rubber component in this case include: the addition amount of the ethylene-propylene copolymer, the ethylene-butene copolymer, the ethylene-propylene-butene copolymer, etc. may be set to 1 to 30% by mass, more preferably 5 to 10% by mass.

(1C) Laminated layer

The (1C) laminate layer constituting the laminate film of the first invention of the present application may be optionally or desirably laminated with other layers such as a (1D) base material layer described later.

Therefore, the (1C) laminated layer is preferably designed in consideration of the lamination strength with other layers and the like.

From this viewpoint, the linear low-density polyethylene derived from petroleum in the (1C) laminated layer is more preferably selected appropriately to have excellent affinity with other layers such as the (1D) base material layer, and the content is more preferably 40 to 99 mass%, particularly preferably 70 to 95 mass%.

In order to further improve the lamination strength with other layers, the surface of the (1C) laminated layer (the surface opposite to the surface laminated with the (1B) intermediate layer) may be subjected to a treatment such as corona treatment or roughening treatment.

On the other hand, from the viewpoint of storing the anti-blocking agent in the laminated film or the like of the first invention of the present application, the (1C) laminated layer may contain the anti-blocking agent.

The anti-blocking agent may suitably be powdered silica, more preferably synthetic silica or the like. From the viewpoint of uniformly dispersing the powdery silica in the (1C) laminated layer, the powdery silica may be dispersed in a resin excellent in the compatibility with the linear low-density polyethylene derived from petroleum constituting the (1C) laminated layer, for example, dispersed in the low-density polyethylene to form a master batch, and then the master batch may be added to the linear low-density polyethylene derived from petroleum. Further, a slip agent (slip agent) may be optionally blended in the laminate layer within a range not detracting from the object of the first invention of the present application.

Slip agents may be exemplified: various amides such as palmitamide, stearamide, oleamide, erucamide, oil palmitamide, stearpalmitamide, methylenebisstearamide, methylenebisoleamide, ethylenebisoleamide, and ethylenebiserucamide; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; hydrogenated castor oil, etc.

(1C) The thickness of the laminated layer is not particularly limited, but is preferably 5 μm or more, particularly preferably 10 μm or more, from the viewpoint of lamination processability and the like.

On the other hand, from the viewpoint of film strength and the like, it is more preferably 30 μm or less, particularly preferably 20 μm or less.

Laminated film

The laminated film according to the first aspect of the present invention comprises: each of which contains a heat-sealed layer (1A), an intermediate layer (1B) and a laminated layer (1C) of linear low-density polyethylene derived from petroleum. In the laminated film of the first invention of the present application, it is preferable that the (1C) laminated layer and the (1A) heat-welded layer are laminated with the (1B) interlayer interposed therebetween, but other layers may be present.

The laminated film of the first invention of the present application can be formed by various generally known film forming methods, for example: a method in which a laminated film is formed by molding films to be (1C) laminated layers, (1B) intermediate layers and (1A) heat-welded layers, respectively, and then bonding the films; a method in which a composite layer film composed of (1B) an intermediate layer and (1A) a heat-seal layer is obtained by using a multilayer stamper, and then (1C) a laminate layer is pressed onto the intermediate layer of (1B) to form a laminate film; a method in which a composite layer film composed of a (1C) laminated layer and a (1B) intermediate layer is obtained by using a multilayer stamper, and then a (1A) heat-seal layer is pressed against the (1B) intermediate layer to form a laminated film; or a method in which a multilayer film comprising (1C) a laminated layer, (1B) an intermediate layer and (1A) a heat-seal layer is obtained by using a multilayer stamper.

The film forming method may be any of various generally known film forming methods, specifically, a T-die cast film forming method and an inflation film forming method.

The laminated film and each layer constituting the laminated film of the first invention of the present application may be an unextended film (non-stretched film) or an stretched film.

The thickness of each layer of the laminated film of the first invention is not particularly limited, but is usually 3 μm or more, more preferably 5 to 150 μm, and particularly preferably in the range of 5 to 90 μm.

The thickness of the laminated film of the first invention is not particularly limited, and is usually 20 μm or more, more preferably 25 μm or more, and particularly preferably 30 μm or more from the viewpoint of securing practical strength or the like. On the other hand, for example, it is usually 200 μm or less, preferably 180 μm or less, and more preferably 150 μm or less, from the viewpoint of practical flexibility even after lamination with the (1D) base material layer.

The laminated film of the first invention contains 3 mass% or more of a plant-derived biopolyethylene in at least one of the (1A) heat-sealed layer, the (1B) intermediate layer, and the (1C) laminated layer.

The laminated film of the first invention has a remarkable technical effect by greatly improving the tearability of the film while maintaining the excellent properties of the conventional polyethylene-based laminated film such as mechanical strength and blocking resistance by containing 3 mass% or more of the plant-derived biopolyethylene in at least one of the heat-seal layer (1A), the intermediate layer (1B) and the laminated layer (1C).

As described above, in the laminated film according to the first aspect of the present invention, when a predetermined amount of plant-derived biopolyethylene is added to any one of the layers constituting the laminated film, the tearability is greatly improved, while the decrease in mechanical strength is suppressed, for example, the yield point stress is not only substantially equal but also improved when no biopolyethylene is added. Therefore, for example, when the laminated film according to the first aspect of the present invention is used in a packaging bag, the easy-to-open property can be greatly improved without impairing the strength of the packaging bag.

The content of the plant-derived biopolyethylene is preferably 6% by mass or more, and particularly preferably 12% by mass or more.

The content of the plant-derived biopolyethylene is not particularly limited, but is preferably 6 mass% or more, particularly preferably 12 mass% or more, from the viewpoints of tearability, film strength and the like.

The laminated film of the first invention of the present application may contain 3 mass% or more of the plant-derived biopolyethylene in at least one of the (1A) heat-seal layer, the (1B) intermediate layer, and the (1C) laminated layer, and preferably contains 3 mass% or more of the plant-derived biopolyethylene in the (1B) intermediate layer, from the viewpoint of the effect of improving the tearability.

Particularly preferably, the plant-derived biopolyethylene is contained in an amount of 3 mass% or more in all of the (1A) heat-seal layer, (1B) intermediate layer and (1C) laminated layer.

The content of the plant-derived biopolyethylene can be appropriately increased or decreased by adjusting the formulation of the resin composition at the time of producing each layer, for example.

The content of plant-derived biopolyethylene in each layer of the film after production can be controlled, for example, by radioactive carbon @, for example ¹⁴ C) Is carried out on the content of biomass-derived carbon in the membraneAnd from this measurement result, the content of biomass-derived carbon in the plant-derived biomass polyethylene was calculated.

The laminated film of the first invention of the present application can reduce the amount of fossil fuel used in the production and reduce the environmental load by containing 3 mass% or more of the plant-derived biopolyethylene in at least one of the (1A) heat-seal layer, the (1B) intermediate layer, and the (1C) laminated layer.

The quality of the laminated film can be calculated by weight-averaging the quality of each layer by the weight of each layer.

The multilayer film can be appropriately increased or decreased in the degree of the quality by adjusting the quality of each layer, and the degree of the quality of the resin used in each layer and the material used for the same can be appropriately increased or decreased.

The multilayer film of the first invention has a biological property of preferably 5 mass% or more, particularly preferably 10 mass% or more.

The higher the degree of the quality of the laminated film of the first invention, the more preferable the higher the degree of the quality, the more preferable the higher the upper limit, and the lower the higher the degree of the quality of the laminated film, from the viewpoint of physical properties of the laminated film, cost and the like, the higher the degree of the quality of the laminated film, and the lower the higher the degree of the quality.

The heat of fusion Δh of the laminated film of the first invention of the present application is preferably 135 to 164J/g, calculated from the melting curve obtained by DSC measurement, at 0 to 130 ℃.

By setting the heat of fusion Δh of 0 ℃ to 130 ℃ in the above range, the tearability of the laminated film can be further effectively improved.

The measurement of the melting curve by DSC and the calculation of the melting heat Δh from 0 ℃ to 130 ℃ in the melting curve can be performed by a conventionally generally known method, and more specifically, can be performed by the method described in the examples of the present application, for example.

The heat of fusion ΔH at 0℃to 130℃is particularly preferably 135 to 164J/g, particularly preferably 140 to 164J/g.

The heat of fusion Δh at 0 ℃ to 130 ℃ can be reduced by adding components other than linear low density polyethylene derived from petroleum, etc., to reduce the crystallinity of the film. More preferably, a plant-derived biopolyethylene, an ethylene-propylene copolymer, an ethylene-butene copolymer, an ethylene-propylene-butene copolymer, or the like is added as a component other than the petroleum-derived linear low-density polyethylene.

The laminate film of the first invention may be an stretched film or a non-stretched film, and is more preferably an stretched film, particularly preferably a biaxially stretched film, from the viewpoint of improvement of mechanical properties.

The biaxial stretching is suitably a sequential biaxial stretching, simultaneous biaxial stretching, multistage stretching or the like.

The conditions for biaxial stretching include generally known conditions for producing a biaxially stretched film, for example, in the sequential biaxial stretching method, the longitudinal stretching temperature is set to 100 to 145 ℃, the stretching ratio is set to 4 to 7 times, the transverse stretching temperature is set to 150 to 190 ℃, and the stretching ratio is set to 8 to 11 times.

(1D) Substrate layer

The laminated film of the first invention of the present application may be laminated with the (1D) base material layer on the (1C) laminated layer, as desired.

(1D) The base layer is not particularly limited, and for example, a film commonly used in plastic packaging bags can be suitably used.

More preferable materials of the (1D) base material layer include, for example: polyolefins such as crystalline polypropylene, crystalline propylene-ethylene copolymer, crystalline polybutene-1, crystalline poly-4-methylpentene-1, low-density-, medium-density-or high-density polyethylene, ethylene-vinyl acetate copolymer (EVA: ethylene Vinyl Acetate), ethylene-ethyl acrylate copolymer (EEA: ethylene Ethyl Acrylate), and ionomer; aromatic ethylene copolymers such as polystyrene and styrene-butadiene copolymers; halogenated ethylene polymers such as polyvinyl chloride and vinylidene chloride resins; nitrile polymers such as acrylonitrile-styrene copolymers and acrylonitrile-styrene-butadiene copolymers; polyamides such as nylon 6, nylon 66, paraxylylene adipamide or metaxylylene adipamide; polyesters such as polyethylene terephthalate (PET: polyethylene Terephthalate) and polybutylene terephthalate; various polycarbonates; plastic films comprising thermoplastic resins such as polyacetal, e.g., polyoxymethylene. In addition, when the packaged content is sensitive to oxygen, a film formed by vapor deposition of a metal oxide or the like, a film coated with an organic compound, or a layer formed of an ethylene-vinyl alcohol copolymer (EVOH: ethylene Vinyl Alcohol Copolymer) resin may be provided on the film.

The plastic film made of these materials may be used without stretching, or may be monoaxially stretched or biaxially stretched.

(1D) The base material layer may be formed by laminating two or more kinds of these plastic films, or may be formed by bonding one or more kinds of these plastic films to a metal foil such as aluminum, paper, or celluloid (Cellophane).

More preferable (1D) substrate layers include, for example: a single layer film composed of an extended nylon film and an extended polyester film; a film comprising a double layer of a polyolefin film such as low-density polyethylene or polypropylene and PET; a film formed of three layers of PET/nylon/polyethylene, and the like are laminated. In the production of these laminated films, an adhesive or anchoring agent (also referred to as a fixing accelerator) may be optionally interposed between the layers. In addition, an ink layer exhibiting a design feel may also be provided.

The method of laminating the (1D) base material layer on the (1C) laminate layer is not particularly limited, and for example, the (1D) base material layer may be directly laminated on the (1C) laminate layer by extrusion lamination or the like. The (1D) base material layer may be laminated on the (1C) laminated layer via an adhesive by dry lamination or the like. As the adhesive, generally used adhesives such as urethane adhesives, acid-modified polyolefin adhesives, polyester adhesives, polyether adhesives, and polyamide adhesives can be used.

(1D) The thickness of the base material layer may be arbitrarily set, and is generally selected from the range of 5 to 50. Mu.m, more preferably from the range of 10 to 30. Mu.m.

The laminated film of the first invention of the present application and the laminated film in which the (1D) base material layer is laminated on the (1C) laminated layer of the laminated film of the first invention of the present application are suitable for use in various applications, and are particularly suitable for use as a packaging material.

When used as a packaging material, the laminated films or the laminated films and other films are heat-sealed to each other on the heat-seal layer (1A) to form a packaging bag.

In the package bag with a tear port, the clip chain package bag, or the like, the package bag is torn at the time of opening, and therefore the laminate film of the first invention of the present invention, which has significantly improved tearability, can be particularly suitably used.

The contents contained in these packaging bags are not particularly limited, and can be suitably contained in food materials such as vegetables and fruits, processed foods, medicines, sanitary products, and the like.

Embodiments of the second invention of the present application are specifically described below.

The second aspect of the present invention is a laminated film comprising: a laminated film comprising (2A) a heat-seal layer, (2B) an intermediate layer and (2C) a laminated layer of linear low-density polyethylene derived from petroleum, wherein the intermediate layer (2B) contains a plant-derived biopolyethylene.

That is, the laminated film according to the second invention of the present application contains linear low density polyethylene derived from petroleum in each of the (2A) heat-seal layer, (2B) intermediate layer and (2C) laminated layer.

The laminated film system of the second invention of the present application contains a predetermined amount of plant-derived biopolyethylene in at least the intermediate layer of (2B).

Linear low density polyethylene from petroleum

The linear low-density polyethylene derived from petroleum used in the second invention may be a homopolymer of ethylene produced using petroleum as a raw material or a copolymer of ethylene and an α -olefin produced using petroleum as a raw material, and may be a linear low-density polyethylene derived from petroleum synthesized by a generally known production method.

From petroleumThe linear low density polyethylene may be commercially available, for example 2040F (C6-LLDPE, MFR;4.0, density; 0.918 g/cm) manufactured by Ube-Maruzen Polyethylene Co., ltd ³ )。

The linear low density polyethylene derived from petroleum preferably has a density of 0.905 to 0.935g/cm ³ Particularly preferably from 0.915 to 0.930g/cm ³ The MFR is more preferably 0.5 to 6.0g/10 min, particularly preferably 2.0 to 4.0g/10 min.

The linear low density polyethylene derived from petroleum preferably has a molecular weight distribution (expressed as a ratio of weight average molecular weight: mw to number average molecular weight: mn: mw/Mn) in the range of 1.5 to 4.0, more preferably in the range of 1.8 to 3.5. This Mw/Mn can be determined by Gel Permeation Chromatography (GPC).

The linear low density polyethylene derived from petroleum has 1 to more sharp peaks as measured from an endothermic curve of a Differential Scanning Calorimeter (DSC) at a heating rate of 10 ℃/min, and the peak maximum temperature, that is, the melting point is preferably in the range of 95 to 140 ℃, more preferably in the range of 105 to 130 ℃.

The linear low density polyethylene derived from petroleum can be produced by a conventionally known production method using: catalysts generally known in the past include multi-site catalysts such as chiffon catalysts and single-site catalysts such as metal aromatic catalysts. From the viewpoint of obtaining a linear low-density polyethylene which can form a film having a narrow molecular weight distribution and a high strength, it is more preferable to use a single-site catalyst.

In the above transition metal compound of group IV of the periodic Table containing a ligand having a cyclopentadienyl skeleton, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group or the like. The substituted cyclopentadienyl group is a group having at least one substituent selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms, a silane group-substituted alkyl group, a silane group-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group, a halogen group, a haloalkyl group, a halosilane group, and the like. The substituted cyclopentadienyl group may have 2 or more substituents, and in addition, the substituents may be bonded to each other to form a ring, thereby forming an indene ring, a fluorene ring, an azulene ring, a hydrogenated body thereof, and the like. The rings formed by bonding substituents to each other may further have substituents to each other.

Among the transition metal compounds of group IV of the periodic Table containing a ligand having a cyclopentadienyl skeleton, zirconium, titanium, hafnium, etc., particularly zirconium, hafnium, etc., are cited as the transition metal. The transition metal compound generally has 2 ligands having a cyclopentadienyl skeleton, and each of the ligands having a cyclopentadienyl skeleton is preferably bonded to each other through a crosslinking group. Further, crosslinking groups may be exemplified by: substituted silylene groups such as alkylene group, silylene group, dialkylsilylene group and diarylsilene group having 1 to 4 carbon atoms, substituted germylene groups such as dialkylgermylene group and diarylgeneylene group, and the like. More preferably a substituted silylene group.

By co-catalyst is meant that the transition metal compound of group IV of the periodic Table is effectively formed into a polymerization catalyst or that ionic charge in an activated state on the catalyst is made uniform. The auxiliary catalyst can be exemplified by: benzene-soluble aluminoxane or benzene-insoluble organoaluminum oxy compound of organoaluminum oxy compound, ion-exchange layered silicate, boron compound, ionic compound composed of cation containing or not containing active hydrogen group and noncoordinating anion, lanthanoid salt such as lanthanum oxide, tin oxide, phenoxy compound containing fluorine group, etc.

The transition metal compound of group IV of the periodic Table containing a ligand having a cyclopentadienyl skeleton may be used as a carrier for supporting an inorganic or organic compound. The support is more preferably a porous oxide of an inorganic or organic compound, and specifically, examples thereof include: montmorillonite plasma-exchange layered silicate, siO ₂ 、Al ₂ O ₃ 、MgO、ZrO ₂ 、TiO ₂ 、B ₂ O ₃ 、CaO、ZnO、BaO、ThO ₂ Etc. or mixtures of these.

The linear low-density polyethylene derived from petroleum may optionally be formulated with various generally known additives which are usually added to olefin polymers, such as antioxidants, weather stabilizers, antistatic agents, antifogging agents, antiblocking agents, slip agents (slip agents) and the like, within a range not detracting from the object of the second invention of the present application.

Plant-derived biopolyethylene

The plant-derived biopolyethylene used in the second invention of the present application is a polyethylene obtained by polymerizing ethylene produced using a plant as a raw material.

In the second aspect of the present invention, the plant-derived biopolyethylene may be any of high-density polyethylene, low-density polyethylene and linear low-density polyethylene, and is more preferably low-density polyethylene or linear low-density polyethylene, and particularly preferably low-density polyethylene.

The polyethylene from the plant may be a commercial product, and for example, a commercially available polyethylene manufactured by Braskem corporation may be used. Specifically, SL218 and SPB681 may be suitably used.

The plant-derived biopolyethylene used in the second invention is obtained by polymerizing a monomer containing ethylene derived from a living body. The biomass-derived ethylene is preferably ethylene obtained by the following production method, but is not limited thereto. Further, since ethylene derived from biomass is used as a monomer of the raw material, the polyethylene system polymerized is derived from biomass. The raw material monomer of the polyethylene may not contain 100% by mass of ethylene derived from a living organism, and may contain ethylene not derived from a living organism or a raw material monomer other than ethylene.

In the second invention of the present application, the term "biomass-derived fermented ethanol" means ethanol obtained by bringing a microorganism producing ethanol or a product derived from a crushed product thereof into contact with a culture medium containing a carbon source obtained from a plant material, and purifying the resulting culture medium after production. The purification of ethanol from the culture solution may be carried out by a conventionally known method such as distillation, membrane separation and extraction. Examples thereof include a method of adding benzene, cyclohexane, etc. and azeotroping them, and a method of removing water by membrane separation, etc.

Since this dehydration reaction is an endothermic reaction, it is usually carried out under heating. The heating temperature is not limited as long as the reaction is carried out at a commercially useful reaction rate, but is preferably 100℃or higher, more preferably 250℃or higher, and still more preferably 300℃or higher. The upper limit is not particularly limited, and is preferably 500℃or less, more preferably 400℃or less, from the viewpoints of energy balance and equipment.

The reaction pressure is also not particularly limited, and is preferably a pressure of not less than normal pressure in order to facilitate subsequent gas-liquid separation. The fixed bed flow-through reaction in which the separation of the catalyst is easily performed is industrially preferable, but may be a liquid-phase suspension bed, a fluidized bed, or the like.

The carbon number of the α -olefin is not particularly limited, but an α -olefin having 3 to 20 carbon atoms can be generally used, and butene, hexene or octene is more preferable. This is because butene, hexene or octene can be produced by polymerizing ethylene as a raw material derived from biomass. Further, by containing such an α -olefin, the polyolefin polymerized has an alkyl group as a branched structure, and can be constituted as a polyolefin having a higher flexibility than a simple linear polyolefin.

The concentration of ethylene derived from biomass (hereinafter sometimes referred to as "biomass") in the polyethylene is determined by radioactive carbon [ ] ¹⁴ C) Is a value obtained by measuring the content of biomass-derived carbon. It is known that the carbon dioxide in the atmosphere contains the carbon dioxide at a certain ratio (105.5 pMC) ¹⁴ C, plants grown so as to receive carbon dioxide from the atmosphere, e.g. from maize ¹⁴ The C content was also about 105.5pMC. In addition, it is hardly contained in fossil fuels ¹⁴ C is also known. Thus, by measuring the total carbon atoms contained in the polyethylene ¹⁴ The ratio of C can be calculated as the ratio of carbon from the biomass. In the second invention of the present application, in the polyethylene ¹⁴ The content of C is set to P _14C In the case of (2), the content P of biomass-derived carbon _bio This can be obtained in the following manner.

P _bio (％)＝P _14C /105.5×100

In the biomass polyethylene used in the second invention of the present application, theoretically, if all of the ethylene derived from the biomass is used as a raw material of the polyethylene, the ethylene concentration from the biomass is 100%, and the degree of the biomass-derived polyethylene is 100%. Further, the concentration of ethylene derived from biomass in the polyethylene derived from fossil fuel produced only from the raw material derived from fossil fuel was 0%, and the degree of biomass of the polyethylene derived from fossil fuel was 0%.

In the second invention of the present application, the degree of biology of the biopolyethylene is not necessarily 100%. This is because the amount of fossil fuel can be reduced as compared with the prior art even if a raw material derived from biomass is used for a part of the biomass polyethylene.

The method for polymerizing the monomer containing ethylene derived from the biomass in the biopolyethylene used in the second invention of the present application is not particularly limited, and may be carried out by a conventionally known method. The polymerization temperature or polymerization pressure may be appropriately adjusted depending on the polymerization method or polymerization apparatus. The polymerization apparatus is not particularly limited, and conventionally known apparatuses can be used.

The polymerization method of the living polyethylene may be appropriately selected depending on the kind of the intended polyethylene, for example, the density or branching of the High Density Polyethylene (HDPE), the Medium Density Polyethylene (MDPE), the Low Density Polyethylene (LDPE), the Linear Low Density Polyethylene (LLDPE), and the like. For example, it is more preferable to use a multi-site catalyst such as a chiffon catalyst or a phillips catalyst, or a single-site catalyst such as a metal aromatic catalyst as a polymerization catalyst, and to carry out the polymerization in 1-stage or 2-stage or more by any one of gas-phase polymerization, slurry polymerization, solution polymerization and high-pressure ion polymerization.

Various generally known additives, such as antioxidants, weather stabilizers, antistatic agents, antifoggants, antiblocking agents, slip agents (slip agents) and the like, which are usually added to olefin polymers, can be optionally formulated into the plant-derived biopolyethylene within a range not detracting from the object of the second invention of the present application.

The laminated film of the second invention has (2A) a heat-seal layer, (2B) an intermediate layer, and (2C) a laminated layer described below.

(2A) The heat-welded layer, the (2B) intermediate layer and the (2C) laminated layer all contain the linear low-density polyethylene derived from petroleum. By making the (2A) heat-welded layer, (2B) intermediate layer and (2C) laminated layer each contain the linear low-density polyethylene derived from petroleum as described above, the lamination strength between the layers can be made sufficient. Further, the laminated film is advantageous from the viewpoint of productivity and cost.

(2A) Thermal fusion layer

When the packaging bag is formed using the laminated film according to the second aspect of the present invention, the heat-seal layer (2A) constituting the laminated film according to the second aspect of the present invention is often formed as the innermost layer and is welded to another film. Therefore, it is preferable to use a low melting point resin in order to obtain high sealing strength. For example, by setting the ethylene content of the linear low-density polyethylene derived from petroleum to be low, the melting point of the heat-seal layer (2A) can be lowered. More specifically, the ethylene content of the linear low-density polyethylene derived from petroleum is preferably 10 mass% or less, more preferably 7 mass% or less, and even more preferably 5 mass% or less.

When the ethylene content of the linear low-density polyethylene derived from petroleum has to be increased due to the strength of the film or the necessity of using a material common to other layers, etc., a low-melting resin may be added to the (2A) heat-welded layer. In the case where the plant-derived biopolyethylene is added to the heat-sealed layer (2A), the plant-derived biopolyethylene having a low melting point may be added.

The other low-melting point resins mentioned above can be exemplified by: ethylene-based polymers having a relatively low density such as high-pressure low-density polyethylene and ethylene- α -olefin random copolymer; and an adhesion-imparting resin such as an aliphatic hydrocarbon resin, a alicyclic hydrocarbon resin, an aromatic hydrocarbon resin, a polyterpene resin, a rosin, a styrene resin, and a coumarone-indene resin.

The linear low-density polyethylene derived from petroleum in the heat-seal layer (2A) is preferably contained in an amount of 50 mass% or more, more preferably 55 to 99 mass%, particularly preferably 65 to 95 mass%, from the viewpoint of heat sealability and the like.

From the viewpoint of rigidity and the like, the content of the plant-derived biopolyethylene in the (2A) heat-seal layer is preferably 1% by mass or more, more preferably 5 to 40% by mass, particularly preferably 7 to 30% by mass.

(2A) The thickness of the heat-seal layer is not particularly limited, but is preferably 5 μm or more, and more preferably 10 μm or more, from the viewpoint of heat sealability and the like.

Various commonly known additives, such as an antiblocking agent, a slip agent (slip agent), an antioxidant, a weather-resistant stabilizer, an antistatic agent, an antifogging agent, etc., which are generally added to polyolefin, may be optionally blended into the heat-sealing layer within a range not detracting from the object of the second invention of the present application.

(2B) Intermediate layer

Among the layers constituting the laminated film according to the second aspect of the present invention, (2A) the heat-seal layer is preferably designed so as to obtain an appropriate seal strength, and (2C) the laminated layer is preferably designed in consideration of the lamination strength with (2D) the base material layer and the like, whereas (2B) the limitation of the intermediate layer is relatively small, so that desired physical properties such as mechanical properties and performance can be preferentially imparted to the entire laminated film according to the second aspect of the present invention. In this case, the thickness of the intermediate layer (2B) is preferably set to be larger than the thickness of the heat-seal layer (2A) and the thickness of the laminated layer (2C), and particularly preferably set to be larger than the sum of the thickness of the heat-seal layer (2A) and the thickness of the laminated layer (2C).

More specifically, the thickness of the intermediate layer (2B) is more preferably 10 μm or more, particularly preferably 15 μm or more, and particularly preferably 30 μm or more.

On the other hand, from the viewpoint of heat sealability and the like, the thickness of the intermediate layer (2B) is preferably 150 μm or less, more preferably 130 μm or less, still more preferably 100 μm or less, and particularly preferably 90 μm or less.

For example, from the viewpoint of achieving high mechanical strength for the entire laminate, the (2B) intermediate layer is more preferably a resin having high mechanical strength at a high ratio. For example, a resin having a high molecular weight and a narrow molecular weight distribution is selected as the linear low density polyethylene derived from petroleum, and the content is more preferably set to be high.

From this viewpoint, the content of the linear low-density polyethylene derived from petroleum in the heat-seal layer (2A) is more preferably 50% by mass or more, particularly preferably 75 to 100% by mass, particularly preferably 85 to 100% by mass, and particularly preferably 90 to 100% by mass.

From the viewpoint of improving flexibility and impact resistance of the entire laminate, the intermediate layer (2B) is preferably a resin having high flexibility and impact resistance at a high ratio. For example, a resin having high flexibility and impact resistance may be selected as the linear low density polyethylene derived from petroleum, and the content may be further set to be high.

Further, the flexibility and impact resistance of the intermediate layer (2B) can be improved by adding an elastomer or rubber component to the intermediate layer (2B), and the flexibility and impact resistance of the entire laminate can be improved. Examples of the elastomer or rubber component in this case include: the addition amount of the ethylene-propylene copolymer, the ethylene-butene copolymer, the ethylene-propylene-butene copolymer, etc. may be set to 1 to 30% by mass, more preferably 5 to 10% by mass.

(2C) Laminated layer

The (2C) laminate layer constituting the laminate film of the second invention of the present application may be optionally or desirably laminated with other layers such as a (2D) base material layer described later.

Therefore, the (2C) laminated layer is preferably designed in consideration of the lamination strength with other layers and the like.

From this viewpoint, the linear low-density polyethylene derived from petroleum in the (2C) laminated layer is more preferably selected appropriately to have excellent affinity with other layers such as the (2D) base material layer, and the content is more preferably 40 to 99 mass%, particularly preferably 70 to 95 mass%.

In order to further improve the lamination strength with other layers, the surface of the (2C) laminated layer (the surface opposite to the surface laminated with the (2B) intermediate layer) may be subjected to a treatment such as corona treatment or roughening treatment.

On the other hand, from the viewpoint of storing the anti-blocking agent in the laminated film or the like of the second invention of the present application, the (2C) laminated layer may contain the anti-blocking agent.

The anti-blocking agent may suitably be powdered silica, more preferably synthetic silica or the like. From the viewpoint of uniformly dispersing the powdery silica in the (2C) laminated layer, the powdery silica may be dispersed in a resin excellent in the compatibility with the linear low-density polyethylene derived from petroleum constituting the (2C) laminated layer, for example, dispersed in the low-density polyethylene to form a master batch, and then the master batch may be added to the linear low-density polyethylene derived from petroleum. Further, a slip agent (slip agent) may be optionally blended in the laminate layer within a range not to impair the object of the second invention of the present application.

(2C) The thickness of the laminated layer is not particularly limited, but is preferably 5 μm or more, particularly preferably 10 μm or more, from the viewpoint of lamination processability and the like.

(2A) Any of the heat-sealing layer, the (2B) intermediate layer, and the (2C) laminated layer may be added with various additives and fillers other than the linear low-density polyethylene derived from petroleum (and the plant-derived biopolyethylene when present), for example, a heat stabilizer, an antioxidant, a light stabilizer, an antistatic agent, an antiblocking agent, a lubricant, a nucleating agent, a flame retardant, a pigment, a dye, calcium carbonate, barium sulfate, magnesium hydroxide, mica, talc, clay, an antibacterial agent, an antifogging agent, and the like, as long as the object of the second invention of the present application is not violated. Other thermoplastic resins, thermoplastic elastomers, rubbers, hydrocarbon resins, petroleum resins, and the like may be blended within a range that does not violate the object of the second invention of the present application.

Laminated film

The laminated film according to the second aspect of the present invention comprises: each of which contains a heat-welded layer (2A) and an intermediate layer (2B) of linear low-density polyethylene derived from petroleum and a laminated layer (2C). In the laminated film according to the second aspect of the present invention, the (2C) laminated layer and the (2A) heat-welded layer are preferably laminated with the (2B) interlayer interposed therebetween, but other layers may be present.

The laminate film of the second invention of the present application can be formed by various generally known film forming methods, such as: a method in which a laminated film is formed by molding films, which are the laminated layer (2C), the intermediate layer (2B) and the heat-seal layer (2A), respectively, and then bonding the films; a method in which a composite layer film composed of (2B) an intermediate layer and (2A) a heat-seal layer is obtained by using a multilayer stamper, and then (2C) a laminate layer is pressed onto the intermediate layer surface of (2B) to form a laminate film; a method in which a composite layer film composed of a (2C) laminated layer and a (2B) intermediate layer is obtained by using a multilayer stamper, and then a (2A) heat-seal layer is pressed against the (2B) intermediate layer to form a laminated film; or a method in which a multilayer film comprising (2C) a laminated layer, (2B) an intermediate layer and (2A) a heat-seal layer is obtained by using a multilayer stamper.

The laminated film and each layer constituting the laminated film of the second invention of the present application may be an unextended film (non-stretched film) or an stretched film.

The thickness of each layer of the laminated film of the second invention is not particularly limited, but is usually 3 μm or more, more preferably 5 to 150 μm, and particularly preferably in the range of 5 to 90 μm.

The thickness of the laminated film of the second invention is not particularly limited, and is usually 20 μm or more, more preferably 25 μm or more, and particularly preferably 30 μm or more from the viewpoint of securing practical strength or the like. On the other hand, for example, it is usually 200 μm or less, preferably 180 μm or less, and more preferably 150 μm or less, from the viewpoint of practical flexibility even after lamination with a (2D) base material.

The laminated film of the second invention of the present application contains a plant-derived biopolyethylene in the intermediate layer (2B). By incorporating the plant-derived biopolyethylene in the intermediate layer (2B), the laminated film of the second invention of the present application can greatly improve the significant technical effect of achieving young's modulus while maintaining the excellent properties of the conventional polyethylene-based laminated film such as the blocking resistance. The laminate film of the second invention is particularly advantageous for applications such as self-standing bags where high mechanical strength is required, because the young's modulus is greatly improved.

(2B) The content of the plant-derived biopolyethylene in the intermediate layer is preferably 3% by mass or more, more preferably 4.4% by mass or more, still more preferably 10% by mass or more, and particularly preferably 15% by mass or more.

(2B) The content of the plant-derived biopolyethylene in the intermediate layer is not particularly limited, but is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less, from the viewpoint of burst resistance and the like.

The laminated film of the second invention of the present application may contain a plant-derived biopolyethylene in the (2B) intermediate layer, but from the viewpoint of further increasing young's modulus and further reducing environmental load, it is more preferable that the plant-derived biopolyethylene is also contained in the (2A) heat-seal layer and/or the (2C) laminated layer. It is particularly preferable that all of the layers (2A), the (2B) intermediate layer and the (2C) laminated layer contain a plant-derived biopolyethylene.

(2A) The content of the plant-derived biopolyethylene in the heat fusion layer and/or the (2C) laminate layer is preferably 10 mass% or more, and particularly preferably 20 mass% or more.

(2A) The content of the plant-derived biopolyethylene in the heat fusion layer and/or the (2C) laminate layer is not particularly limited, but is usually 50 mass% or less, more preferably 30 mass% or less, and particularly preferably 25 mass% or less from the viewpoint of burst resistance and the like.

The content of the plant-derived biopolyethylene in the laminated film of the second invention is preferably 6% by mass or more, and particularly preferably 12% by mass or more.

The content of the plant-derived biopolyethylene in the laminated film of the second invention is not particularly limited, but is preferably generally 30 mass% or less from the viewpoints of tearability, film strength, and the like.

The content of plant-derived biopolyethylene in each layer of the film after manufacture can be determined, for example, by irradiationSexual carbon ¹⁴ C) The content of the biomass-derived carbon in the film is measured, and is calculated from the measurement result and the content of the biomass-derived carbon in the plant-derived biomass polyethylene.

The laminated film according to the second aspect of the present invention contains a plant-derived biopolyethylene in (2B) the intermediate layer (and more preferably (2A) the heat-seal layer and/or (2C) the laminated layer), thereby reducing the amount of fossil fuel used in production and reducing environmental load.

The quality of the laminated film can be appropriately increased or decreased by adjusting the quality of each layer, and the quality of each layer can be appropriately increased or decreased by adjusting the quality of the resin used in each layer and the amount thereof.

The multilayer film of the second invention has a biological property of preferably 5 mass% or more, particularly preferably 10 mass% or more.

The higher the degree of the quality of the laminated film of the second invention, the more preferable the higher the degree of the quality, the more preferable the higher the upper limit, and the lower the higher the degree of the quality of the laminated film, from the viewpoint of physical properties of the laminated film, cost and the like, the higher the degree of the quality of the laminated film, and the lower the higher the degree of the quality.

The heat of fusion Δh of the laminated film of the second invention of the present application is preferably 135 to 164J/g, calculated from the melting curve obtained by DSC measurement, at 0 to 130 ℃.

By making the heat of fusion Δh of 0 ℃ to 130 ℃ lie in the above range, the young's modulus of the laminated film can be further effectively raised.

The laminate film of the second invention may be an stretched film or a non-stretched film, and is more preferably an stretched film, particularly preferably a biaxially stretched film, from the viewpoint of improvement of mechanical properties.

(2D) Substrate layer

The laminated film of the second invention of the present application may be laminated with the (2D) base material layer on the (2C) laminated layer, as desired.

(2D) The base layer is not particularly limited, and for example, a film commonly used in plastic packaging bags can be suitably used.

More preferred materials for the (2D) substrate layer include, for example: polyolefins such as crystalline polypropylene, crystalline propylene-ethylene copolymer, crystalline polybutene-1, crystalline poly-4-methylpentene-1, low-density-, medium-density-or high-density polyethylene, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and ionomer; aromatic ethylene copolymers such as polystyrene and styrene-butadiene copolymers; halogenated ethylene polymers such as polyvinyl chloride and vinylidene chloride resins; nitrile polymers such as acrylonitrile-styrene copolymers and acrylonitrile-styrene-butadiene copolymers; polyamides such as nylon 6, nylon 66, paraxylylene adipamide or metaxylylene adipamide; polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate; various polycarbonates; plastic films comprising thermoplastic resins such as polyacetal, e.g., polyoxymethylene. In addition, when the packaged content is sensitive to oxygen, a film formed by vapor deposition of a metal oxide or the like, a film coated with an organic compound, or a layer formed of an ethylene-vinyl alcohol copolymer (EVOH) resin may be provided on the film.

(2D) The base material layer may be a single layer or a laminate of two or more of these plastic films, or may be formed by bonding one or more of these plastic films to a metal foil such as aluminum, paper, or celluloid (Cellophane).

More preferred (2D) substrate layers include, for example: a single layer film composed of an extended nylon film and an extended polyester film; a film comprising a double layer of a polyolefin film such as low-density polyethylene or polypropylene and PET; a film formed of three layers of PET/nylon/polyethylene, and the like are laminated. In the production of these laminated films, an adhesive or an anchor agent may be optionally interposed between the layers. In addition, an ink layer exhibiting a design feel may also be provided.

The method of laminating the (2D) base material layer on the (2C) laminate layer is not particularly limited, and for example, the (2D) base material layer may be directly laminated on the (2C) laminate layer by extrusion lamination or the like. The (2D) base material layer may be laminated on the (2C) laminated layer via an adhesive by dry lamination or the like. As the adhesive, generally used adhesives such as urethane adhesives, acid-modified polyolefin adhesives, polyester adhesives, polyether adhesives, and polyamide adhesives can be used.

(2D) The thickness of the base material layer may be arbitrarily set, and is generally selected from the range of 5 to 50. Mu.m, more preferably from the range of 10 to 30. Mu.m.

The laminated film according to the second aspect of the present invention and the laminated film obtained by laminating the (2D) base material layer on the (2C) laminated layer of the laminated film according to the second aspect of the present invention are suitable for various applications, and particularly suitable for use as a packaging material.

When used as a packaging material, the laminated films or the laminated films and other films are heat-sealed to each other on the heat-seal layer (2A) to form a packaging bag.

The laminate film of the second invention is improved in young's modulus, so that the packaging bag is easy to stand up, and can be suitably used as a stand-up pouch, for example.

The content of the packaging bag, more preferably a self-supporting bag, which is to be contained in the laminated film according to the second invention of the present application is not particularly limited, but is particularly suitable for containing, for example, a liquid-like chemical agent, a cosmetic product such as a liquid detergent or a softener, a liquid or powder detergent such as a liquid food such as espresso, or a powder such as sugar, pepper, salt.

Embodiments of the third invention of the present application are specifically described below.

The third aspect of the present invention is a laminated film comprising: the laminated film comprising (3A) a heat-sealed layer, (3B) an intermediate layer and (3C) a laminated layer of linear low-density polyethylene derived from petroleum, wherein at least one of the (3A) heat-sealed layer, (3B) the intermediate layer and (3C) the laminated layer contains at least 3% or more of a plant-derived linear low-density polyethylene.

That is, the laminated film according to the third invention of the present application contains linear low density polyethylene derived from petroleum in each of the (3A) heat-seal layer, (3B) intermediate layer and (3C) laminated layer.

The laminated film according to the third aspect of the present invention contains a predetermined amount of a plant-derived biomass linear low-density polyethylene in at least one of the (3A) heat-seal layer, the (3B) intermediate layer, and the (3C) laminated layer.

Linear low density polyethylene from petroleum

The linear low-density polyethylene derived from petroleum used in the third invention may be a homopolymer of ethylene produced using petroleum as a raw material or a copolymer of ethylene and an α -olefin produced using petroleum as a raw material, and may be a linear low-density polyethylene derived from petroleum synthesized by a generally known production method.

The linear low density polyethylene derived from petroleum is commercially available, for example 2040F (C6-LLDPE, MFR;4.0, density; 0.918 g/cm) manufactured by Ube-Maruzen Polyethylene Co., ltd ³ )。

In the above transition metal compound of group IV of the periodic Table containing a ligand having a cyclopentadienyl skeleton, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group or the like. The substituted cyclopentadienyl group has at least one substituent selected from the group consisting of a hydrocarbon group having 1 to 30 carbon atoms, a silane group-substituted alkyl group, a silane group-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group, a halogen group, a haloalkyl group, a halosilane group, and the like. The substituted cyclopentadienyl group may have 2 or more substituents, and in addition, the substituents may be bonded to each other to form a ring, thereby forming an indene ring, a fluorene ring, an azulene ring, a hydrogenated body thereof, and the like. The rings formed by bonding substituents to each other may further have substituents to each other.

The linear low-density polyethylene derived from petroleum may optionally be formulated with various generally known additives which are usually added to olefin polymers, such as antioxidants, weather stabilizers, antistatic agents, antifogging agents, antiblocking agents, slip agents (slip agents) and the like, within a range not detracting from the object of the third invention of the present application.

Plant-derived biomass linear low density polyethylene

The plant-derived linear low-density polyethylene used in the third invention is a linear low-density polyethylene obtained by polymerizing ethylene produced using a plant as a raw material.

In the third aspect of the present invention, the plant-derived linear low-density polyethylene is linear low-density polyethylene, and is obtained by polymerizing a monomer containing ethylene derived from a living body as described below.

Therefore, it is more preferable that the linear low density polyethylene obtained by polymerizing a monomer containing ethylene derived from a biomass has the same physical properties as the conventional linear low density polyethylene.

For example, "linear low density polyethylene" in the present application is more preferably a vinyl (co) polymer having 10 to 30 SCBs (side chains of 1 to 5 carbon atoms; also referred to as "short chain branches") per 1000 carbon atoms.

The plant-derived biomass linear low-density polyethylene may be commercially available, and for example, plant-derived biomass linear low-density polyethylene manufactured and sold by the Braskem company may be used. In particular, model names may be suitably used: SL218.

The plant-derived linear low-density polyethylene used in the third invention is obtained by polymerizing a monomer containing ethylene derived from a biomass. The biomass-derived ethylene is preferably obtained by the following production method, but is not limited thereto. Further, since ethylene derived from biomass is used as a monomer of the raw material, the linear low-density polyethylene obtained by polymerization is derived from biomass. The raw material monomer of the linear low-density polyethylene may not contain 100 mass% of ethylene derived from a biomass, and may contain ethylene not derived from a biomass or a raw material monomer other than ethylene.

The method for producing the biomass ethylene which is a raw material of the plant-derived biomass linear low-density polyethylene is not particularly limited, and can be obtained by a conventionally generally known method. An example of a method for producing bioethylene will be described below.

In the third invention of the present application, the term "biomass-derived fermented ethanol" means ethanol obtained by bringing a microorganism producing ethanol or a product derived from a crushed product thereof into contact with a culture medium containing a carbon source obtained from a plant material, and purifying the resulting culture medium after production. The purification of ethanol from the culture solution may be carried out by a conventionally known method such as distillation, membrane separation and extraction. Examples thereof include a method of adding benzene, cyclohexane, etc. and azeotroping them, and a method of removing water by membrane separation, etc.

When ethylene is obtained by dehydration of ethanol, a catalyst is usually used, and the catalyst is not particularly limited, and a conventionally known catalyst can be used. In the process, a fixed bed flow-through reaction that facilitates separation of the catalyst from the product is advantageous, and for example, gamma-alumina is more preferable.

The monomer used as a raw material of the plant-derived biomass linear low-density polyethylene may further contain ethylene and/or α -olefin derived from fossil fuel, or may further contain α -olefin derived from biomass.

The carbon number of the α -olefin is not particularly limited, but an α -olefin having 3 to 20 carbon atoms can be generally used, and butene, hexene or octene is more preferable. This is because butene, hexene or octene can be produced by polymerizing ethylene as a raw material derived from biomass. Further, the linear low-density polyethylene obtained by polymerizing the α -olefin has an alkyl group as a branched structure, and can be formed into a polyethylene having a higher flexibility than a simple linear polyethylene.

The linear low-density polyethylene is more preferably a copolymer of ethylene and an α -olefin derived from ethylene in terms of environmental load. This is because ethylene, which is a raw material derived from biomass, can be theoretically produced from 100% of components derived from biomass.

The concentration of ethylene derived from biomass (hereinafter sometimes referred to as "biomass") in the linear low-density polyethylene is determined by radioactive carbon ¹⁴ C) Is a value obtained by measuring the content of biomass-derived carbon. It is known that the carbon dioxide in the atmosphere contains the carbon dioxide at a certain ratio (105.5 pMC) ¹⁴ C, plants grown so as to receive carbon dioxide from the atmosphere, e.g. from maize ¹⁴ The C content was also about 105.5pMC. In addition, it is hardly contained in fossil fuels ¹⁴ C is also known. Therefore, by measuring the total carbon atoms contained in the linear low density polyethylene ¹⁴ The ratio of C can be calculated as the ratio of carbon from the biomass. In the third invention of the present application, in the linear low density polyethylene ¹⁴ The content of C is set to P _14C In the case of (2), the content P of biomass-derived carbon _bio This can be obtained in the following manner.

P _bio (％)＝P _14C /105.5×100

In the linear low density polyethylene of the biomass used in the third invention of the present application, theoretically, if ethylene derived from the biomass and α -olefin derived therefrom are all used as the raw material of the polyethylene, the ethylene concentration from the biomass is 100%, and the degree of the biomass of the linear low density polyethylene derived from the biomass is 100%. Further, the concentration of ethylene derived from biomass in the polyethylene derived from fossil fuel produced only from the raw material derived from fossil fuel was 0%, and the degree of biomass of the polyethylene derived from fossil fuel was 0%.

In the third invention of the present application, the biomass of the linear low density polyethylene is not necessarily 100%. This is because the amount of fossil fuel can be reduced as compared with the conventional method even if a raw material derived from biomass is used for a part of the biomass linear low-density polyethylene.

The method for polymerizing the biomass-derived ethylene-containing monomer in the biomass-based low-density polyethylene used in the third invention of the present application is not particularly limited, and may be carried out by a conventionally generally known method. The polymerization temperature or polymerization pressure may be appropriately adjusted depending on the polymerization method or polymerization apparatus. The polymerization apparatus is not particularly limited, and conventionally known apparatuses can be used.

The polymerization method of the biomass linear low density polyethylene can be appropriately selected according to the density or branching of the intended linear low density polyethylene. For example, it is more preferable to use a multi-site catalyst such as a chiffon catalyst or a phillips catalyst, or a single-site catalyst such as a metal aromatic catalyst as a polymerization catalyst, and to carry out the polymerization in 1-stage or 2-stage or more by any one of gas-phase polymerization, slurry polymerization, solution polymerization and high-pressure ion polymerization.

From the viewpoint of obtaining a biomass linear low-density polyethylene having a wide molecular weight distribution and excellent flexibility and moldability, it is more preferable to use a multi-site catalyst such as a chiffon catalyst or a phillips catalyst.

The density of the plant-derived biomass linear low-density polyethylene is not particularly limited, and is more preferably 0.905 to 0.935g/cm ³ Particularly preferably from 0.915 to 0.930g/cm ³ 。

The MFR of the plant-derived biomass linear low-density polyethylene is also not particularly limited, but is preferably from 0.3 to 15.0g/10 min, more preferably from 1.0 to 12.0g/10 min, still more preferably from 1.5 to 10.0g/10 min, particularly preferably from 2.0 to 9.0g/10 min, from the viewpoint of moldability and the like.

The molecular weight distribution of the plant-derived biomass linear low-density polyethylene is not particularly limited, and from the viewpoints of flexibility, moldability and the like, the molecular weight distribution (expressed as a ratio of weight average molecular weight: mw to number average molecular weight: mn: mw/Mn) is preferably 3.5 or more, more preferably 3.8 to 9.0, and still more preferably in the range of 4.0 to 8.6. This Mw/Mn can be measured by Gel Permeation Chromatography (GPC), and more specifically, can be measured by, for example, the methods described in the examples of the present application.

In addition, the plant-derived biomass linear low density polyethylene has 1 to more sharp peaks in an endothermic curve measured by a Differential Scanning Calorimeter (DSC) at a heating rate of 10 ℃/min, and the peak has a highest temperature, that is, a melting point, of more preferably 95 to 140 ℃, and still more preferably in the range of 100 to 135 ℃.

The plant-derived biomass linear low-density polyethylene may be used alone or in combination of two or more. In addition, other vinyl polymers (whether from plants or not) may be used along with other polymers.

Various generally known additives, such as antioxidants, weather stabilizers, antistatic agents, antifogging agents, antiblocking agents, slip agents (slip agents) and the like, which are usually added to olefin polymers, can be optionally blended into the plant-derived biomass linear low density polyethylene within a range that does not impair the object of the third invention of the present application.

The laminated film of the third invention of the present application has (3A) a heat-seal layer, (3B) an intermediate layer, and (3C) a laminated layer described below.

(3A) The heat-welded layer, the (3B) intermediate layer and the (3C) laminated layer all contain the linear low-density polyethylene derived from petroleum. By making the (3A) heat-welded layer, (3B) intermediate layer and (3C) laminated layer each contain the linear low-density polyethylene derived from petroleum as described above, the lamination strength between the layers can be made sufficient. Further, the laminated film is advantageous from the viewpoint of productivity and cost.

(3A) Thermal fusion layer

When the packaging bag is formed using the laminated film according to the third aspect of the present invention, the heat-seal layer (3A) constituting the laminated film according to the third aspect of the present invention is often formed as the innermost layer and is welded to another film. Therefore, it is preferable to use a low melting point resin in order to obtain high sealing strength. For example, by setting the ethylene content of the linear low density polyethylene derived from petroleum to be low, the melting point of the heat-welded layer (3A) can be reduced. More specifically, the ethylene content of the linear low-density polyethylene derived from petroleum is preferably 10 mass% or less, more preferably 7 mass% or less, and even more preferably 5 mass% or less.

When the ethylene content of the linear low-density polyethylene derived from petroleum has to be increased due to the strength of the film or the necessity of using a material common to other layers, etc., a low-melting resin may be added to the (3A) heat-welded layer. In the case where the plant-derived biomass linear low-density polyethylene is added to the heat-welded layer (3A), the plant-derived biomass linear low-density polyethylene having a low melting point may be added.

The linear low-density polyethylene derived from petroleum in the heat-sealing layer (3A) is preferably contained in an amount of 50 mass% or more, more preferably 55 to 99 mass%, particularly preferably 65 to 95 mass%, from the viewpoint of heat sealability and the like.

(3A) The thickness of the heat-seal layer is not particularly limited, but is preferably 5 μm or more, and more preferably 10 μm or more, from the viewpoint of heat sealability and the like.

Various commonly known additives, such as an antiblocking agent, a slip agent (slip agent), an antioxidant, a weather-resistant stabilizer, an antistatic agent, an antifogging agent, etc., which are generally added to polyolefin, may be optionally blended into the heat-sealing layer within a range not detracting from the object of the third invention of the present application.

(3B) Intermediate layer

Among the layers constituting the laminated film of the third invention of the present application, (3A) the heat-seal layer is preferably designed so as to obtain an appropriate seal strength, and (3C) the laminated layer is preferably designed in consideration of the lamination strength with the (3D) base material layer or the like, whereas (3B) the limitation of the intermediate layer is relatively small, so that desired physical properties such as mechanical properties and performance can be preferentially imparted to the entire laminated film of the third invention of the present application. In this case, the thickness of the intermediate layer (3B) is preferably set to be larger than the thickness of the heat-seal layer (3A) and the thickness of the laminated layer (3C), and particularly preferably set to be larger than the sum of the thickness of the heat-seal layer (3A) and the thickness of the laminated layer (3C).

More specifically, the thickness of the intermediate layer (3B) is more preferably 10 μm or more, particularly preferably 15 μm or more, and particularly preferably 30 μm or more.

On the other hand, from the viewpoint of heat sealability and the like, the thickness of the intermediate layer (3B) is preferably 150 μm or less, more preferably 130 μm or less, still more preferably 100 μm or less, and 90. Mu.m

For example, from the viewpoint of achieving high mechanical strength for the entire laminate, the (3B) intermediate layer is more preferably a resin having high mechanical strength at a high ratio. For example, a resin having a high molecular weight and a narrow molecular weight distribution is selected as the linear low density polyethylene derived from petroleum, and the content is more preferably set to be high.

From this viewpoint, the content of the linear low-density polyethylene derived from petroleum in the (3A) heat-seal layer is more preferably 50% by mass or more, particularly preferably 75 to 100% by mass, particularly preferably 85 to 100% by mass, and particularly preferably 90 to 100% by mass.

From the viewpoint of improving flexibility and impact resistance of the entire laminate, the intermediate layer (3B) is preferably a resin having high flexibility and impact resistance at a high ratio. For example, a resin having high flexibility and impact resistance may be selected as the linear low density polyethylene derived from petroleum, and the content may be further set to be high.

Further, the flexibility and impact resistance of the intermediate layer (3B) can be improved by adding an elastomer or rubber component to the intermediate layer (3B), and the flexibility and impact resistance of the entire laminate can be improved. Examples of the elastomer or rubber component in this case include: the addition amount of the ethylene-propylene copolymer, the ethylene-butene copolymer, the ethylene-propylene-butene copolymer, etc. may be set to 1 to 30% by mass, more preferably 5 to 10% by mass.

(3C) Laminated layer

The (3C) laminate layer constituting the laminate film of the third invention of the present application may be optionally or desirably laminated with other layers such as a (3D) base material layer described later.

Therefore, the (3C) laminated layer is preferably designed in consideration of the lamination strength with other layers and the like.

From this viewpoint, the linear low-density polyethylene derived from petroleum in the (3C) laminated layer is more preferably selected appropriately to have excellent affinity with other layers such as the (3D) base material layer, and the content is more preferably 40 to 99 mass%, particularly preferably 70 to 95 mass%.

In order to further improve the lamination strength with other layers, the surface of the (3C) lamination layer (the surface opposite to the surface laminated with the (3B) intermediate layer) may be subjected to a treatment such as corona treatment or roughening treatment.

On the other hand, from the viewpoint of storing the anti-blocking agent in the laminated film or the like of the third invention of the present application, the (3C) laminated layer may contain the anti-blocking agent.

The anti-blocking agent may suitably be powdered silica, more preferably synthetic silica or the like. From the viewpoint of uniformly dispersing the powdery silica in the (3C) laminated layer, the powdery silica may be dispersed in a resin excellent in the compatibility with the linear low-density polyethylene derived from petroleum constituting the (3C) laminated layer, for example, dispersed in the low-density polyethylene to form a master batch, and then the master batch may be added to the linear low-density polyethylene derived from petroleum. Further, a slip agent (slip agent) may be optionally blended in the laminate layer within a range not to impair the object of the third invention of the present application.

(3C) The thickness of the laminated layer is not particularly limited, but is preferably 5 μm or more, particularly preferably 10 μm or more, from the viewpoint of lamination processability and the like.

(3A) Any of the heat-sealing layer, the (3B) intermediate layer, and the (3C) laminated layer may be added with various additives and fillers other than the linear low-density polyethylene derived from petroleum (and the biomass linear low-density polyethylene derived from plants when present), for example, a heat stabilizer, an antioxidant, a light stabilizer, an antistatic agent, an antiblocking agent, a lubricant, a nucleating agent, a flame retardant, a pigment, a dye, calcium carbonate, barium sulfate, magnesium hydroxide, mica, talc, clay, an antibacterial agent, an antifogging agent, and the like, as long as the object of the third invention of the present application is not violated. Other thermoplastic resins, thermoplastic elastomers, rubbers, hydrocarbon resins, petroleum resins, and the like may be blended within a range that does not violate the object of the third invention of the present application.

Laminated film

The laminated film according to the third aspect of the present invention comprises: each of which contains a heat-welded layer (3A) and an intermediate layer (3B) of linear low-density polyethylene derived from petroleum and a laminated layer (3C). In the laminated film according to the third aspect of the present invention, the (3C) laminated layer and the (3A) heat-welded layer are preferably laminated with the (3B) interlayer interposed therebetween, but other layers may be present.

The laminated film of the third invention of the present application can be formed by various generally known film forming methods, for example: a method in which a laminated film is formed by molding films to be the laminated layer (3C), the intermediate layer (3B) and the heat-seal layer (3A), and then bonding the films; a method in which a composite layer film composed of (3B) an intermediate layer and (3A) a heat-seal layer is obtained by using a multilayer stamper, and then (3C) a laminate layer is pressed onto the intermediate layer surface of (3B) to form a laminate film; a method in which a composite layer film composed of a (3C) laminated layer and a (3B) intermediate layer is obtained by using a multilayer stamper, and then a (3A) heat-seal layer is pressed against the (3B) intermediate layer to form a laminated film; or a method of using a multilayer stamper to obtain a laminated film comprising (3C) a laminated layer, (3B) an intermediate layer and (3A) a heat-seal layer.

The laminated film and each layer constituting the laminated film of the third invention of the present application may be an unextended film (non-stretched film) or an stretched film.

The thickness of each layer of the laminated film of the third invention is not particularly limited, but is usually 3 μm or more, more preferably 5 to 150 μm, and particularly preferably in the range of 5 to 90 μm.

The thickness of the laminated film of the third invention is not particularly limited, and is usually 20 μm or more, more preferably 25 μm or more, and particularly preferably 30 μm or more from the viewpoint of securing practical strength or the like. On the other hand, for example, it is usually 200 μm or less, preferably 180 μm or less, and more preferably 150 μm or less, from the viewpoint of practical flexibility even after lamination with a (3D) base material.

The laminated film of the third invention of the present application contains 3 mass% or more of a plant-derived biomass linear low-density polyethylene in at least one of the (3A) heat-seal layer, the (3B) intermediate layer, and the (3C) laminated layer.

The laminated film of the third invention has a remarkable technical effect by containing 3 mass% or more of a plant-derived biomass linear low-density polyethylene in at least one of the (3A) heat-seal layer, the (3B) intermediate layer, and the (3C) laminated layer, while maintaining excellent properties of conventional polyethylene-based laminated films such as mechanical strength and blocking resistance, and by greatly improving the lamination strength with the (3D) base material layer described later. Further, even if the lamination strength with the multilayer is greatly improved, surprisingly, the blocking resistance between the laminated films of the third invention of the present application can be maintained at the same level as that of the conventional products.

The content of the plant-derived biomass linear low-density polyethylene is preferably 6 mass% or more, and particularly preferably 12 mass% or more.

The content of the plant-derived biomass linear low-density polyethylene is not particularly limited, but is preferably 6 mass% or more, particularly preferably 12 mass% or more, from the viewpoints of tearability, film strength, and the like.

The laminated film of the third invention of the present application may contain 3 mass% or more of the plant-derived biomass linear low-density polyethylene in at least one of the (3A) heat-sealed layer, the (3B) intermediate layer, and the (3C) laminated layer, and preferably contains 3 mass% or more of the plant-derived biomass linear low-density polyethylene in all of the (3A) heat-sealed layer, the (3B) intermediate layer, and the (3C) laminated layer, in view of the effect of improving the lamination strength.

The content of the plant-derived biomass linear low-density polyethylene can be appropriately increased or decreased by adjusting the formulation of the resin composition at the time of producing each layer, for example.

The content of the plant-derived biomass linear low-density polyethylene in each layer of the film after production can be controlled, for example, by radioactive carbon @, for example ¹⁴ C) The content of the biomass-derived carbon in the film was measured, and the content of the biomass-derived carbon in the plant-derived linear low-density polyethylene was calculated from the measurement result.

The laminated film of the third aspect of the present invention can reduce the amount of fossil fuel used in the production and reduce the environmental load by including the plant-derived biomass linear low-density polyethylene in at least one of the (3A) heat-seal layer, the (3B) intermediate layer, and the (3C) laminated layer.

The multilayer film of the third invention of the present application has a biological property of preferably 5 mass% or more, particularly preferably 10 mass% or more.

The higher the degree of the quality of the laminated film according to the third aspect of the present invention, the higher the quality, the more preferably the higher the upper limit, and the higher the quality of the laminated film, the higher the quality of the laminated film, and the higher the quality of the laminated film, and the higher the quality of the laminated film.

The heat of fusion Δh of the laminated film of the third invention of the present application is preferably 135 to 164J/g, calculated from the melting curve obtained by DSC measurement, at 0 to 130 ℃.

By setting the heat of fusion Δh of 0 ℃ to 130 ℃ in the above range, the lamination strength of the laminated film and the base material layer can be further effectively improved.

As described above, the heat of fusion ΔH at 0℃to 130℃is more preferably 135 to 164J/g, particularly preferably 140 to 164J/g.

The melting point of the laminate film of the third invention corresponding to the maximum peak in the melting curve obtained by DSC measurement is more preferably more than 114 ℃.

By setting the maximum peak value to be within the above range, the lamination strength of the laminated film and the base material layer can be further effectively improved.

The melting point is particularly preferably 115℃or higher, and particularly preferably 116℃or higher.

The laminate film of the third invention may be an stretched film or a non-stretched film, and is more preferably an stretched film, particularly preferably a biaxially stretched film, from the viewpoint of improvement of mechanical properties.

(3D) Substrate layer

The laminated film of the third invention of the present application may be laminated with the (3D) base material layer on the (3C) laminated layer, as desired. In the third invention of the present application, a significant effect of greatly improving the lamination strength with the (3D) base material layer at this time is achieved.

Lamination strength can be measured by a conventionally known method. More specifically, for example, in a (3C) laminate layer of a laminate, after lamination with a (3D) base material layer, a sample may be cut into 15mm wide strips, and then the (3D) base material layer and the laminate may be peeled at an extension speed of 100mm/min, and the strength of the extended peeled surface may be measured for evaluation, more specifically, by the method described in the examples of the present application. The lamination strength at this time is more preferably 3 (N/15 mm) or more, and particularly preferably 5 (N/15 mm) or more.

(3D) The base layer is not particularly limited, and for example, a film commonly used in plastic packaging bags can be suitably used.

Preferred materials for the (3D) substrate layer include, for example: polyolefins such as crystalline polypropylene, crystalline propylene-ethylene copolymer, crystalline polybutene-1, crystalline poly-4-methylpentene-1, low-density-, medium-density-or high-density polyethylene, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and ionomer; aromatic ethylene copolymers such as polystyrene and styrene-butadiene copolymers; halogenated ethylene polymers such as polyvinyl chloride and vinylidene chloride resins; nitrile polymers such as acrylonitrile-styrene copolymers and acrylonitrile-styrene-butadiene copolymers; polyamides such as nylon 6, nylon 66, paraxylylene adipamide or metaxylylene adipamide; polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate; various polycarbonates; plastic films comprising thermoplastic resins such as polyacetal, e.g., polyoxymethylene. In addition, when the packaged content is sensitive to oxygen, a film formed by vapor deposition of a metal oxide or the like, a film coated with an organic compound, or a layer formed of an ethylene-vinyl alcohol copolymer (EVOH) resin may be provided on the film.

(3D) The base material layer may be a single layer or two or more kinds of plastic films stacked, or one or two or more kinds of plastic films may be bonded to a metal foil such as aluminum, paper, or a celluloid.

More preferred (3D) substrate layers include, for example: a single layer film composed of an extended nylon film and an extended polyester film; a film comprising a double layer of a polyolefin film such as low-density polyethylene or polypropylene and PET; a film formed of three layers of PET/nylon/polyethylene, and the like are laminated. In the production of these laminated films, an adhesive or an anchor agent may be optionally interposed between the layers. In addition, an ink layer exhibiting a design feel may also be provided.

The method of laminating the (3D) base material layer on the (3C) laminate layer is not particularly limited, and for example, the (3D) base material layer may be directly laminated on the (3C) laminate layer by extrusion lamination or the like. The (3D) base material layer may be laminated on the (3C) laminated layer via an adhesive by dry lamination or the like. As the adhesive, generally used adhesives such as urethane adhesives, acid-modified polyolefin adhesives, polyester adhesives, polyether adhesives, and polyamide adhesives can be used.

(3D) The thickness of the base material layer may be arbitrarily set, and is generally selected from the range of 5 to 50. Mu.m, more preferably from the range of 10 to 30. Mu.m.

The laminated film according to the third aspect of the present invention and the laminated film obtained by laminating the (3D) base material layer on the (3C) laminated layer of the laminated film according to the third aspect of the present invention are suitable for various applications, and particularly suitable for use as a packaging material.

When used as a packaging material, the laminated films or the laminated films and other films are heat-sealed to each other on the heat-seal layer (3A) to form a packaging bag.

The laminated film in which the (3D) base material layer is laminated on the (3C) laminated layer of the laminated film according to the third invention has a high lamination strength, and is less likely to be peeled off during production and use, and therefore, is suitable for use as a packaging material in a wide range of applications in combination with various (3D) base material layers.

The content to be contained in the packaging bag using the laminated film according to the third invention of the present application is not particularly limited, but is particularly suitable for containing food materials such as vegetables and fruits, food products for conditioning, liquid medicines, cosmetic products such as liquid detergents and softeners, liquid or powder detergents such as liquid foods such as espresso, and powders such as sugar, pepper, salt.

Examples (example)

Hereinafter, the first to third inventions of the present application will be specifically described with reference to examples/comparative examples. In addition, the first to third inventions of the present application are not limited to the following examples in any sense.

The evaluation of physical properties and characteristics in examples and comparative examples of the first invention of the present application was performed by the following method.

(1) Molecular weight distribution (Mw/Mn)

After the polymer sample was subjected to pretreatment under the following conditions, the molecular weight was measured by GPC, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) was set as the molecular weight distribution.

i) Pretreatment of

20mL of mobile phase (o-dichlorobenzene) for GPC measurement was added to a sample (30 mg) and subjected to vibration dissolution at 145℃and then the resulting solution was subjected to thermal filtration through a sintered filter sheet having a pore size of 1.0 μm, followed by supplying to GPC measurement.

ii)GPC

The device comprises: HLC-8321 of Tosoh Co., ltd., gel permeation chromatograph

And (3) pipe column: tosoh Co., ltd., inner diameter 7.5 mm. Times.30 cm, 4 (TSKgel GMH6-HT:2, TSKgel GMH6-HTL: 2)

Column temperature: 140 DEG C

A detector: differential refractometer

Flow rate: 1mL/min

Sampling interval: 0.5 second

(2) Heat of fusion

The sample was subjected to a fine balance of about 5mg using a Q100 (R) as a Differential Scanning Calorimeter (DSC) manufactured by TA Instruments, according to JISK7121 and under nitrogen inflow: at 50 mL/min, at a heating rate: the temperature was raised from 25℃to 250℃at 10℃per minute, the thermal melting curve was measured, and the heat of crystallization and melting of the sample were obtained from the obtained thermal melting curve.

(3) Tensile strength (yield point stress)

An elongation stress-strain curve was produced by using a Tensilon universal material tester (RTG 1210, manufactured by A & D Co., ltd.) and performing an elongation test on a film test piece having a width of 15mm at an elongation speed of 300 mm/min while setting the space between the clamps to 50mm at an ambient temperature of 23℃in the main elongation direction (main shrinkage direction) and the right-angle direction of the film. The first maximum point portion of the extended stress-strain curve is used as the yield point stress (unit: MPa).

(4) Tear strength

The tear strength in the MD and TD directions of the laminated films obtained in examples and comparative examples were measured using a light-load tear tester manufactured by Toyo Seisakusho Co., ltd.) under conditions of a measurement temperature of 23.+ -. 3 ℃ and a measurement humidity of 50.+ -. 5% RH.

Comparative example a1

The components constituting each layer were supplied to each extruder by the formulation shown in table 1, and were produced by T-compression molding: a laminated film having (1A) a heat-seal layer, (1B) an intermediate layer, and (1C) a laminated layer, which were composed of the same layers as shown in table 1. Since no biopolyethylene derived from a plant was used, the degree of biomass was 0 mass%.

The films produced were evaluated for heat of fusion, tensile strength (yield point stress) and tear strength. The results are shown in Table 1.

Examples a1 to a12

A laminated film was produced in the same manner as in comparative example a1 except that a plant-derived biopolyethylene or the like was used and the resin composition was changed as shown in table 1, and heat of fusion, elongation (yield point stress) and tear strength were evaluated. The results are shown in Table 1.

Details of the respective components described in the column for resin composition in table 1 of the first invention of the present application are described below.

·LLDPE(1)

Linear low density polyethylene from petroleum

MFR(2.16kg、190℃)：2.3g/10min

Density: 918kg/m ³

Molecular weight distribution (Mw/Mn): 2.52

Biomass PE (1)

Plant-derived biomass low density polyethylene

MFR(2.16kg、190℃)：3.8g/10min

Density: 922kg/m ³

Molecular weight distribution (Mw/Mn): 5.88

TABLE 1

The evaluation of physical properties and characteristics in examples, comparative examples and reference examples of the second invention of the present application was performed by the following methods.

(1) Molecular weight distribution (Mw/Mn)

i) Pretreatment of

ii)GPC

The device comprises: HLC-8321 of Tosoh Co., ltd., gel permeation chromatograph

Column temperature: 140 DEG C

A detector: differential refractometer

Flow rate: 1mL/min

Sampling interval: 0.5 second

(2) Heat of fusion

The sample was subjected to a fine balance of about 5mg using a Q100 (R) as a Differential Scanning Calorimeter (DSC) manufactured by TA Instruments, according to JISK7121 and under nitrogen inflow: at 50 mL/min, at a heating rate: the temperature was raised from 25℃to 200℃at 10℃per minute, the thermal melting curve was measured, and the heat of crystallization and melting of the sample were obtained from the obtained thermal melting curve.

(3) Young's modulus

An elongated film sheet (length: 150mm, width: 15 mm) was cut out from the film in the Machine Direction (MD) and the Transverse Direction (TD) as a test piece, and an elongation tester (manufactured by A & D Co., ltd., RTG 1210) was used, and the distance between the clamps was set to be: 100mm, crosshead speed: extension tests were performed at 5 mm/min and Young's modulus (MPa) was determined. The measurement value was an average value of 5 times.

Comparative example b1

The components constituting each layer were supplied to each extruder by the formulation shown in table 2, and were produced by T-compression molding: a laminated film comprising (2A) a heat-welded layer, (2B) an intermediate layer, and (2C) a laminated layer each having a resin composition shown in table 2 and also comprising the layers shown in table 2. Since no biopolyethylene derived from a plant was used, the degree of biomass was 0 mass%.

The heat of fusion and young's modulus were evaluated for the films produced. The results are shown in Table 2.

(reference examples b2 to b5 and examples b1 to b 8)

A laminate film was produced in the same manner as in comparative example b1 except that a plant-derived biopolyethylene or the like was used and the resin composition was changed as shown in table 2, and heat of fusion and young's modulus were evaluated. The results are shown in Table 2.

Details of the respective components described in the column for resin composition in table 2 of the second invention of the present application are described below.

·LLDPE(2)

Linear low density polyethylene from petroleum

MFR(2.16kg、190℃)：2.3g/10min

Density: 918kg/m ³

Molecular weight distribution (Mw/Mn): 2.52

Biomass PE (2)

Plant-derived biomass low density polyethylene

MFR(2.16kg、190℃)：3.8g/10min

Density: 922kg/m ³

Molecular weight distribution (Mw/Mn): 5.88

TABLE 2

The evaluation of physical properties and characteristics in examples and comparative examples of the third invention of the present application was performed by the following method.

(1) Molecular weight distribution (Mw/Mn)

i) Pretreatment of

ii)GPC

The device comprises: HLC-8321 of Tosoh Co., ltd., gel permeation chromatograph

Column temperature: 140 DEG C

A detector: differential refractometer

Flow rate: 1mL/min

Sampling interval: 0.5 second

(2) Melting point, heat of fusion

The sample was subjected to a fine balance of about 5mg using a Q100 (R) as a Differential Scanning Calorimeter (DSC) manufactured by TA Instruments, according to JISK7121 and under nitrogen inflow: at 50 mL/min, at a heating rate: the melting point (Tm) and the heat of crystal fusion of the sample were obtained from the obtained thermal melting curve by measuring the thermal melting curve at 10℃per minute from 25℃to 200 ℃.

(3) Caking Strength

The heat-welded layers (3A) of the laminated films were laminated to each other according to ASTM D1893-67.

(4) Lamination strength

Nylon film (trade name: harren, manufactured by eastern spinning corporation) having a thickness of 15 μm was used as the (3D) base material layer. An adhesive (adhesive prepared by mixing tikoku chemical company, takelac/takenate=a310/A3 in ethyl acetate) was then applied to the (3C) laminate layer side surface of the laminate as a sample, and was adhered to the (3D) substrate layer by a manual laminator. The sample was cut into a 15mm wide long strip, a peeling opening was formed between the laminate as a sample and the (3D) base material layer, and then the base material and the sealant were peeled off by using a Tensilon universal material tester (manufactured by a & D corporation, RTG 1210), and the strength of the extended peeled surface was measured at an extension speed of 100mm/min, and this was set as the lamination strength (N/15 mm).

Comparative example c1

The components constituting each layer were supplied to each extruder by the formulation shown in table 3, and were produced by T-compression molding: a laminated film comprising (3A) a heat-welded layer, (3B) an intermediate layer, and (3C) a laminated layer composed of the same layers as shown in table 3 and having the resin composition shown in table 3. Since no biomass linear low density polyethylene from a plant was used, the biomass was 0 mass%.

The produced film was evaluated for melting point, heat of fusion, blocking strength and lamination strength. The results are shown in Table 3.

Examples c1 to c8

A laminated film was produced in the same manner as in comparative example c1 except that a plant-derived biomass linear low-density polyethylene or the like was used and the resin composition was changed as shown in table 3, and the melting point, heat of fusion, blocking strength and lamination strength were evaluated. The results are shown in Table 3.

Details of the respective components described in the column for resin composition in table 3 of the third invention of the present application are described below.

·LLDPE(3)

Linear low density polyethylene from petroleum

MFR(2.16kg、190℃)：2.3g/10min

Density: 918kg/m ³

Molecular weight distribution (Mw/Mn): 2.52

Biomass PE (3)

Plant-derived biomass linear low density polyethylene

MFR(2.16kg、190℃)：2.3g/10min

Density: 916kg/m ³

Molecular weight distribution (Mw/Mn): 4.12

TABLE 3

Industrial applicability

The laminated film of the first invention is highly useful for packaging bags such as tear-off packaging bags and clip chain packaging bags, particularly in various fields of agriculture, food processing industry, distribution, and external food industry, because it has high-level and practically high-value properties, particularly in the case of using the laminated film in packaging bags such as tear-off packaging bags and clip chain packaging bags, while maintaining excellent properties such as mechanical strength.

The laminated film according to the second aspect of the present invention is particularly useful for packaging bags such as stand-alone bags, and has extremely high applicability in various fields of agriculture, food processing industry, distribution, and food industry, because it has high practical value at a high level, such as a mechanical property such as young's modulus, which is important when using packaging bags such as stand-alone bags, and also has a reduced environmental load when manufacturing the laminated film, while maintaining the excellent properties of conventional polyethylene laminated films.

The laminated film of the third aspect of the present invention has extremely high applicability in various fields of industries such as agriculture, food processing industry, distribution, and exterior food, and is particularly suitable for use in packaging bags and the like, since it has properties of high value in practice at a high level, such as a great improvement in lamination strength with a film on the outer layer side, and also a reduction in environmental load during production thereof, while maintaining the excellent characteristics of conventional polyethylene laminated films.

Claims

1. A laminated film, comprising: the heat-sealed layer (1A), the intermediate layer (1B) and the laminated layer (1C) each containing a linear low-density polyethylene derived from petroleum, wherein at least one of the heat-sealed layer (1A), the intermediate layer (1B) and the laminated layer (1C) contains 3 mass% or more of a plant-derived biopolyethylene.

2. The laminated film according to claim 1, wherein the heat of fusion Δh of 0 ℃ to 130 ℃ calculated from a melting curve obtained by DSC measurement is 135 to 164J/g.

3. The laminated film according to claim 1 or 2, wherein the molecular weight distribution Mw/Mn of the plant-derived biopolyethylene is 3.5 or more.

4. A laminated film according to any one of claims 1 to 3, wherein the (1D) base material layer is provided on the side of the (1C) laminated layer directly or via an adhesive layer.

5. A packaging bag constituted by the laminated film according to any one of claims 1 to 4.

6. The package of claim 5 which is a peel-off package.

7. The package of claim 5 which is a zipper package.

8. A laminated film, comprising: the heat-sealing layer (2A), the intermediate layer (2B) and the laminated layer (2C) respectively contain linear low-density polyethylene derived from petroleum, wherein the intermediate layer (2B) contains plant-derived biopolyethylene.

9. The laminated film according to claim 8, wherein the heat of fusion Δh of 0 ℃ to 130 ℃ calculated from a melting curve obtained by DSC measurement is 135 to 164J/g.

10. The laminated film according to claim 8 or 9, wherein the molecular weight distribution Mw/Mn of the plant-derived biopolyethylene is 3.5 or more.

11. The laminated film according to any one of claims 8 to 10, wherein (2A) the heat-welded layer, (2B) the intermediate layer, and (2C) the laminated layer each contain a plant-derived biopolyethylene.

12. The laminated film according to any one of claims 8 to 11, wherein a (2D) base material layer is provided on the side of the (2C) laminated layer directly or via an adhesive layer.

13. A packaging bag comprising the laminated film according to any one of claims 8 to 12.

14. A self-standing pouch comprising the laminated film according to any one of claims 8 to 12.

15. A laminated film, comprising: the heat-sealed layer (3A), the intermediate layer (3B) and the laminated layer (3C) each contain a linear low-density polyethylene derived from petroleum, and at least 3% or more of the plant-derived linear low-density polyethylene is contained in at least one of the heat-sealed layer (3A), the intermediate layer (3B) and the laminated layer (3C).

16. The laminated film according to claim 15, wherein the (3C) laminated layer contains at least 3% or more of the plant-derived biomass linear low density polyethylene.

17. The laminated film according to claim 15 or 16, wherein the heat of fusion Δh of 0 ℃ to 130 ℃ calculated from the melting curve obtained by DSC measurement is 135 to 164J/g.

18. The laminated film according to any one of claims 15 to 17, wherein the plant-derived biomass linear low-density polyethylene has a molecular weight distribution Mw/Mn of 3.5 or more.

19. The laminated film according to any one of claims 15 to 18, wherein a (3D) base material layer is provided on the side of the (3C) laminated layer directly or via an adhesive layer.

20. A packaging bag comprising the laminated film according to any one of claims 15 to 19.